Colorants and colorant modifiers

Description

TECHNICAL FIELD
The present invention relates to a family of colorants and colorant modifiers. The colorant modifiers, according to the present invention, are capable of stabilizing a color to ordinary light and/or rendering the colorant mutable when exposed to specific wavelengths of electromagnetic radiation.
BACKGROUND OF THE INVENTION
A major problem with colorants is that they tend to fade when exposed to sunlight or artificial light. It is believed that most of the fading of colorants when exposed to light is due to photodegradation mechanisms. These degradation mechanisms include oxidation or reduction of the colorants depending upon the environmental conditions in which the colorant is placed. Fading of a colorant also depends upon the substrate upon which they reside.
Product analysis of stable photoproducts and intermediates has revealed several important modes of photodecomposition. These include electron ejection from the colorant, reaction with ground-state or excited singlet state oxygen, cleavage of the central carbon-phenyl ring bonds to form amino substituted benzophenones, such as triphenylmethane dyes, reduction to form the colorless leuco dyes and electron or hydrogen atom abstraction to form radical intermediates.
Various factors such as temperature, humidity, gaseous reactants, including O.sub.2, O.sub.3, SO.sub.2, and NO.sub.2, and water soluble, nonvolatile photodegradation products have been shown to influence fading of colorants. The factors that effect colorant fading appear to exhibit a certain amount of interdependence. It is due to this complex behavior that observations for the fading of a particular colorant on a particular substrate cannot be applied to colorants and substrates in general.
Under conditions of constant temperature it has been observed that an increase in the relative humidity of the atmosphere increases the fading of a colorant for a variety of colorant-substrate systems (e.g., McLaren, K., J. Soc. Dyers Colour, 1956, 72, 527). For example, as the relative humidity of the atmosphere increases, a fiber may swell because the moisture content of the fiber increases. This aids diffusion of gaseous reactants through the substrate structure.
The ability of a light source to cause photochemical change in a colorant is also dependent upon the spectral distribution of the light source, in particular the proportion of radiation of wavelengths most effective in causing a change in the colorant and the quantum yield of colorant degradation as a function of wavelength. On the basis of photochemical principles, it would be expected that light of higher energy (short wavelengths) would be more effective at causing fading than light of lower energy (long wavelengths). Studies have revealed that this is not always the case. Over 100 colorants of different classes were studied and found that generally the most unstable were faded more efficiently by visible light while those of higher lightfastness were degraded mainly by ultraviolet light (McLaren, K., J. Soc. Dyers Colour, 1956, 72, 86).
The influence of a substrate on colorant stability can be extremely important. Colorant fading may be retarded or promoted by some chemical group within the substrate. Such a group can be a ground-state species or an excited-state species. The porosity of the substrate is also an important factor in colorant stability. A high porosity can promote fading of a colorant by facilitating penetration of moisture and gaseous reactants into the substrate. A substrate may also act as a protective agent by screening the colorant from light of wavelengths capable of causing degradation.
The purity of the substrate is also an important consideration whenever the photochemistry of dyed technical polymers is considered. For example, technical-grade cotton, viscose rayon, polyethylene, polypropylene, and polyisoprene are known to contain carbonyl group impurities. These impurities absorb light of wavelengths greater than 300 nm, which are present in sunlight, and so, excitation of these impurities may lead to reactive species capable of causing colorant fading (van Beek, H. C. A., Col. Res. Appl., 1983, 8(3), 176).
Therefore, there exists a great need for methods and compositions which are capable of stabilizing a wide variety of colorants from the effects of both sunlight and artificial light.
There is also a need for colorants that can be mutated, preferably from a colored to a colorless form, when exposed to a specific predetermined wavelength of electromagnetic radiation. For certain uses, the ideal colorant would be one that is stable in ordinary light and can be mutated to a colorless form when exposed to a specific predetermined wavelength of electromagnetic radiation.
SUMMARY OF THE INVENTION
The present invention addresses the needs described above by providing compositions and methods for stabilizing colorants against radiation including radiation in the visible wavelength range. In addition, the present invention provides certain embodiments in which the light-stable colorant system is mutable by exposure to certain narrow bandwidths of radiation. In certain embodiments, the colorant system is stable in ordinary visible light and is mutable when exposed to a specific wavelength of electromagnetic radiation.
In one embodiment, the present invention provides a composition comprising a colorant which, in the presence of a radiation transorber, is mutable when exposed to a specific wavelength of radiation, while at the same time, provides light stability to the colorant when the composition is exposed to sunlight or artificial light. The radiation transorber may be any material which is adapted to absorb radiation and interact with the colorant to effect the mutation of the colorant. Generally, the radiation transorber contains a photoreactor and a wavelength-specific sensitizer. The wavelength-specific sensitizer generally absorbs radiation having a specific wavelength, and therefore a specific amount of energy, and transfers the energy to the photoreactor. It is desirable that the mutation of the colorant be irreversible.
The present invention also relates to colorant compositions having improved stability, wherein the colorant is associated with a modified photoreactor. It has been determined that conventional photoreactors, which normally contain a carbonyl group with a functional group on the carbon alpha to the carbonyl group, acquire the ability to stabilize colorants when the functional group on the alpha carbon is removed via dehydration.
Accordingly, the present invention also includes a novel method of dehydrating photoreactors that have a hydroxyl group in the alpha position to a carbonyl group. This reaction is necessary to impart the colorant stabilizing capability to the photoreactor. The novel method of dehydrating photoreactors that have a hydroxyl group in the alpha position to a carbonyl group can be used with a wide variety of photoreactors to provide the colorant stabilizing capability to the photoreactor. The resulting modified photoreactor can optionally be linked to wavelength-selective sensitizer to impart the capability of decolorizing a colorant when exposed to a predetermined narrow wavelength of electromagnetic radiation. Accordingly, the present invention provides a photoreactor capable of stabilizing a colorant that it is admixed with.
In certain embodiments of the present invention, the mixture of colorant and radiation transorber is mutable upon exposure to radiation. In this embodiment, the photoreactor may or may not be modified as described above to impart stability when admixed to a colorant. In one embodiment, an ultraviolet radiation transorber is adapted to absorb ultraviolet radiation and interact with the colorant to effect the irreversible mutation of the colorant. It is desirable that the ultraviolet radiation transorber absorb ultraviolet radiation at a wavelength of from about 4 to about 300 nanometers. It is even more desirable that the ultraviolet radiation transorber absorb ultraviolet radiation at a wavelength of 100 to 300 nanometers. The colorant in combination with the ultraviolet radiation transorber remains stable when exposed to sunlight or artificial light. If the photoreactor is modified as described above, the colorant has improved stability when exposed to sunlight or artificial light.
Another stabilizer that is considered part of the present invention is an arylketoalkene having the following general formula: ##STR1## wherein R.sub.1 is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;
R.sub.2 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;
R.sub.3 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group; and
R.sub.4 is an aryl, heteroaryl, or substituted aryl group. Preferably, the alkene group is in the trans configuration.
Desirably, the arylketoalkene stabilizing compound has the following formula: ##STR2## which efficiently absorbs radiation having a wavelength at about 308 nanometers, or ##STR3## which efficiently absorbs radiation having a wavelength at about 280 nanometers. Desirably, arylketoalkene stabilizing compound of the present invention is in the trans configuration with respect to the double bond. However, the sensitizer may also be in the cis configuration across the double bond.
Accordingly, this embodiment of the present invention provides a stabilizing molecule, the above arylketoalkene, which when associated with a colorant, stabilizes the colorant. Therefore, the above arylketoalkene can be used as an additive to any colorant composition. For example, as the arylketoalkene compound is poorly soluble in water, it can be directly added to solvent or oil based (not water based) colorant compositions. Additionally, the arylketoalkene compound can be added to other colorant compositions that contain additives enabling the solubilization of the compound therein. Further, the arylketoalkene stabilizing compounds can be solubilized in an aqueous solution by attaching the compound to a large water soluble molecule, such as a cyclodextrin.
In another embodiment of the present invention, the colored composition of the present invention may also contain a molecular includant having a chemical structure which defines at least one cavity. The molecular includants include, but are not limited to, clathrates, zeolites, and cyclodextrins. Each of the colorant and ultraviolet radiation transorber or modified photoreactor or arylketoalkene stabilizing compound can be associated with one or more molecular includant. The includant can have multiple radiation transorbers associated therewith. In other embodiments, the includant can have many modified photoreactors or arylketoalkene stabilizing compounds associated therewith.
In some embodiments, the colorant is at least partially included within a cavity of the molecular includant and the ultraviolet radiation transorber or modified photoreactor or arylketoalkene stabilizer is associated with the molecular includant outside of the cavity. In some embodiments, the ultraviolet radiation transorber or modified photoreactor or arylketoalkene stabilizer is covalently coupled to the outside of the molecular includant.
The present invention also relates to a method of mutating the colorant associated with the composition of the present invention. The method comprises irradiating a composition containing a mutable colorant and an ultraviolet radiation transorber with ultraviolet radiation at a dosage level sufficient to mutate the colorant. As stated above, in some embodiments the composition further includes a molecular includant. In another embodiment, the composition is applied to a substrate before being irradiated with ultraviolet radiation. It is desirable that the mutated colorant is stable.
The present invention is also related to a substrate having an image thereon that is formed by the composition of the present invention. The colorant, in the presence of the radiation transorber or modified photoreactor or arylketoalkene compound, is more stable to sunlight or artificial light. When a molecular includant is included in the composition, the colorant is stabilized by a lower ratio of radiation transorbers to colorant.
The present invention also includes a dry imaging process wherein the imaging process utilizes, for example, the following three mutable colorants: cyan, magenta, and yellow. These mutable colorants can be layered on the substrate or can be mixed together and applied as a single layer. Using, for example, laser technology with three lasers at different wavelengths, an image can be created by selectively "erasing" colorants. A further advantage of the present invention is that the remaining colorants are stable when exposed to ordinary light.
The present invention also includes a method of storing data utilizing the mutable colorant on a substrate, such as a disc. The colorant is selectively mutated using a laser at the appropriate wavelength to provide the binary information required for storing the information. The present invention is particularly useful for this purpose because the unmutated colorant is stabilized to ordinary light by the radiation transorber and can be further stabilized by the optionally included molecular includant.
The present invention also includes data processing forms for use with photo-sensing apparatus that detect the presence of indicia at indicia-receiving locations of the form. The data processing forms are composed of a sheet of carrier material and a plurality of indicia-receiving locations on the surface of the sheet. The indicia-receiving locations are defined by a colored composition including a mutable colorant and a radiation transorber.
These and other features and advantages of the present invention will become apparent after a review of the following detailed description of the disclosed embodiments and the appended claims.

BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 illustrates an ultraviolet radiation transorber/mutable colorant/molecular includant complex wherein the mutable colorant is malachite green, the ultraviolet radiation transorber is IRGACURE.RTM. 184 (1-hydroxycyclohexyl phenyl ketone), and the molecular includant is .beta.-cyclodextrin.
FIG. 2 illustrates an ultraviolet radiation transorber/mutable colorant/molecular includant complex wherein the mutable colorant is Victoria Pure Blue BO (Basic Blue 7), the ultraviolet radiation transorber is IRGACURE.RTM. 184 (1-hydroxycyclohexyl phenyl ketone), and the molecular includant is .beta.-cyclodextrin.
FIG. 3 is a plot of the average number of ultraviolet radiation transorber molecules which are covalently coupled to each molecule of a molecular includant in several colored compositions, which number also is referred to by the term, "degree of substitution," versus the decolorization time upon exposure to 222-nanometer excimer lamp ultraviolet radiation.
FIG. 4 is an illustration of several 222 nanometer excimer lamps arranged in four parallel columns wherein the twelve numbers represent the locations where twelve intensity measurements were obtained approximately 5.5 centimeters from the excimer lamps.
FIG. 5 is an illustration of several 222 nanometer excimer lamps arranged in four parallel columns wherein the nine numbers represent the locations where nine intensity measurements were obtained approximately 5.5 centimeters from the excimer lamps.
FIG. 6 is an illustration of several 222 nanometer excimer lamps arranged in four parallel columns wherein the location of the number "1" denotes the location where ten intensity measurements were obtained from increasing distances from the lamps at that location. (The measurements and their distances from the lamp are summarized in Table 12.)

DETAILED DESCRIPTION OF THE INVENTION
The present invention relates in general to a light-stable colorant system that is optionally mutable by exposure to narrow band-width radiation. The present invention more particularly relates to a composition comprising a colorant which, in the presence of a radiation transorber, is stable under ordinary light but is mutable when exposed to specific, narrow band-width radiation. The radiation transorber is capable of absorbing radiation and interacting with the colorant to effect a mutation of the colorant. The radiation transorber may be any material which is adapted to absorb radiation and interact with the colorant to effect the mutation of the colorant. Generally, the radiation transorber contains a photoreactor and a wavelength-specific sensitizer. The wavelength-specific sensitizer generally absorbs radiation having a specific wavelength, and therefore a specific amount of energy, and transfers the energy to the photoreactor. It is desirable that the mutation of the colorant be irreversible.
The present invention also relates to colorant compositions having improved stability, wherein the colorant is associated with a modified photoreactor. It has been determined that conventional photoreactors which normally contain a carbonyl group with a functional group on the carbon alpha to the carbonyl group acquire the ability to stabilize colorants when the functional group on the alpha carbon is removed. Accordingly, the present invention also includes a novel method of dehydrating photoreactors that have a hydroxyl group in the alpha position to a carbonyl group. This reaction is necessary to impart the colorant stabilizing capability to the photoreactor. The novel method of dehydrating photoreactors that have a hydroxyl group in the alpha position to a carbonyl group can be used with a wide variety of photoreactors to provide the colorant stabilizing capability to the photoreactor. The resulting modified photoreactor can optionally be linked to a wavelength-selective sensitizer to impart the capability of decolorizing a colorant when exposed to a predetermined narrow wavelength of electromagnetic radiation. Accordingly, the present invention provides a photoreactor capable of stabilizing a colorant with which it is admixed.
In certain embodiments of the present invention, the colorant and radiation transorber is mutable upon exposure to radiation. In this embodiment, the photoreactor may or may not be modified as described above to impart stability when admixed to a colorant. In one embodiment, an ultraviolet radiation transorber is adapted to absorb ultraviolet radiation and interact with the colorant to effect the irreversible mutation of the colorant. It is desirable that the ultraviolet radiation transorber absorb ultraviolet radiation at a wavelength of from about 4 to about 300 nanometers. If the photoreactor in the radiation transorber is modified as described above, the colorant has improved stability when exposed to sunlight or artificial light.
The present invention also relates to a method of mutating the colorant in the composition of the present invention. The method comprises irradiating a composition containing a mutable colorant and a radiation transorber with radiation at a dosage level sufficient to mutate the colorant.
The present invention further relates to a method of stabilizing a colorant comprising associating the modified photoreactor described above with the colorant. Optionally, the photoreactor may be associated with a wavelength-selective sensitizer, or the photoreactor may be associated with a molecular includant, or both.
Thus, the stabilizing composition produced by the process of dehydrating a tertiary alcohol that is alpha to a carbonyl group on a photoreactor is shown in the following general formula: ##STR4## wherein R.sub.1 is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;
R.sub.2 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;
R.sub.3 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group; and
R.sub.4 is an aryl, heteroaryl, or substituted aryl group. Preferably, the alkene group is in the trans configuration.
Desirably, the arylketoalkene stabilizing compound is represented by the following formulas: ##STR5##
Accordingly, this embodiment of the present invention provides a stabilizing molecule, the above arylketoalkene, which when associated with a colorant, stabilizes the colorant. Therefore, the above arylketoalkene can be used as an additive to any colorant composition. For example, as the arylketoalkene compound is not water soluble, it can be directly added to solvent or oil based (not water based) colorant compositions. Additionally, the arylketoalkene compound can be added to other colorant compositions that contain additives enabling the solubilization of the compound therein. Further, the arylketoalkene stabilizing compounds can be solubilized in an aqueous solution by attaching the compound to a large water soluble molecule, such as a cyclodextrin.
After definitions of various terms used herein, the mutable colorant composition of the present invention and methods for making and using that composition are described in detail, followed by a detailed description of the improved light stable composition of the present invention and methods for making the improved light stable compositions.
Definitions
The term "composition" and such variations as "colored composition" are used herein to mean a colorant, and a radiation transorber or a modified photoreactor or an arylketoalkene stabilizer. Where the colored composition includes the modified photoreactor, it may further comprise a wavelength-selective sensitizer. Where the colored composition includes the arylketoalkene stabilizer, it may further comprise a photoreactor. When reference is being made to a colored composition which is adapted for a specific application, the term "composition-based" is used as a modifier to indicate that the material includes a colorant, an ultraviolet radiation transorber or a modified photoreactor or an arylketoalkene stabilizer, and, optionally, a molecular includant.
As used herein, the term "colorant" is meant to include, without limitation, any material which typically will be an organic material, such as an organic colorant or pigment. Desirably, the colorant will be substantially transparent to, that is, will not significantly interact with, the ultraviolet radiation to which it is exposed. The term is meant to include a single material or a mixture of two or more materials.
As used herein, the term "irreversible" means that the colorant will not revert to its original color when it no longer is exposed to ultraviolet radiation.
The term "radiation transorber" is used herein to mean any material which is adapted to absorb radiation at a specific wavelength and interact with the colorant to affect the mutation of the colorant and, at the same time, protect the colorant from fading in sunlight or artificial light. The term "ultraviolet radiation transorber" is used herein to mean any material which is adapted to absorb ultraviolet radiation and interact with the colorant to effect the mutation of the colorant. In some embodiments, the ultraviolet radiation transorber may be an organic compound. Where the radiation transorber is comprised of a wavelength-selective sensitizer and a photoreactor, the photoreactor may optionally be modified as described below.
The term "compound" is intended to include a single material or a mixture of two or more materials. If two or more materials are employed, it is not necessary that all of them absorb radiation of the same wavelength. As discussed more fully below, a radiation transorber is comprised of a photoreactor and a wavelength selective sensitizer. The radiation transorber has the additional property of making the colorant with which the radiation transorber is associated light stable to sunlight or aritificial light.
The term "light-stable" is used herein to mean that the colorant, when associated with the radiation transorber or modified photoreactor or arylketoalkene stabilizer molecule, is more stable to light, including, but not limited to, sunlight or artificial light, than when the colorant is not associated with these compounds.
The term "molecular includant," as used herein, is intended to mean any substance having a chemical structure which defines at least one cavity. That is, the molecular includant is a cavity-containing structure. As used herein, the term "cavity" is meant to include any opening or space of a size sufficient to accept at least a portion of one or both of the colorant and the ultraviolet radiation transorber.
The term "functionalized molecular includant" is used herein to mean a molecular includant to which one or more molecules of an ultraviolet radiation transorber or modified photoreactor or arylketoalkene stabilizer are covalently coupled to each molecule of the molecular includant. The term "degree of substitution" is used herein to refer to the number of these molecules or leaving groups (defined below) which are covalently coupled to each molecule of the molecular includant.
The term "derivatized molecular includant" is used herein to mean a molecular includant having more than two leaving groups covalently coupled to each molecule of molecular includant. The term "leaving group" is used herein to mean any leaving group capable of participating in a bimolecular nucleophilic substitution reaction.
The term "artificial light" is used herein to mean light having a relatively broad bandwidth that is produced from conventional light sources, including, but not limited to, conventional incandescent light bulbs and fluorescent light bulbs.
The term "ultraviolet radiation" is used herein to mean electromagnetic radiation having wavelengths in the range of from about 4 to about 400 nanometers. The especially desirable ultraviolet radiation range for the present invention is between approximately 100 to 375 nanometers. Thus, the term includes the regions commonly referred to as ultraviolet and vacuum ultraviolet. The wavelength ranges typically assigned to these two regions are from about 180 to about 400 nanometers and from about 100 to about 180 nanometers, respectively.
The term "thereon" is used herein to mean thereon or therein. For example, the present invention includes a substrate having a colored composition thereon. According to the definition of "thereon" the colored composition may be present on the substrate or it may be in the substrate.
The term "mutable," with reference to the colorant, is used to mean that the absorption maximum of the colorant in the visible region of the electromagnetic spectrum is capable of being mutated or changed by exposure to radiation, preferably ultraviolet radiation, when in the presence of the radiation transorber. In general, it is only necessary that such absorption maximum be mutated to an absorption maximum which is different from that of the colorant prior to exposure to the ultraviolet radiation, and that the mutation be irreversible. Thus, the new absorption maximum can be within or outside of the visible region of the electromagnetic spectrum. In other words, the colorant can mutate to a different color or be rendered colorless. The latter is also desirable when the colorant is used in data processing forms for use with photo-sensing apparatus that detect the presence of indicia at indicia-receiving locations of the form.
Functionalized Molecular Includant
In several embodiments, the radiation transorber molecule, the wavelength-selective sensitizer, the photoreactor, or the arylketoalkene stabilizer may be associated with a molecular includant. It is to be noted that in all the formulas, the number of such molecules can be between approximately 1 and approximately 21 molecules per molecular includant. Of course, in certain situations, there can be more than 21 molecules per molecular includant molecule. Desirably, there are more than three of such molecules per molecular includant.
The degree of substitution of the functionalized molecular includant may be in a range of from 1 to approximately 21. As another example, the degree of substitution may be in a range of from 3 to about 10. As a further example, the degree of substitution may be in a range of from about 4 to about 9.
The colorant is associated with the functionalized molecular includant. The term "associated" in its broadest sense means that the colorant is at least in close proximity to the functionalized molecular includant. For example, the colorant may be maintained in close proximity to the functionalized molecular includant by hydrogen bonding, van der Waals forces, or the like. Alternatively, the colorant may be covalently bonded to the functionalized molecular includant, although this normally is neither desired nor necessary. As a further example, the colorant may be at least partially included within the cavity of the functionalized molecular includant.
The examples below disclose methods of preparing and associating these colorants and ultraviolet radiation transorbers to .beta.-cyclodextrins. For illustrative purposes only, Examples 1, 2, 6, and 7 disclose one or more methods of preparing and associating colorants and ultraviolet radiation transorbers to cyclodextrins.
In those embodiments of the present invention in which the ultraviolet radiation transorber is covalently coupled to the molecular includant, the efficiency of energy transfer from the ultraviolet radiation transorber to the colorant is, at least in part, a function of the number of ultraviolet radiation transorber molecules which are attached to the molecular includant. It now is known that the synthetic methods described above result in covalently coupling an average of two transorber molecules to each molecule of the molecular includant. Because the time required to mutate the colorant should, at least in part, be a function of the number of ultraviolet radiation transorber molecules coupled to each molecule of molecular includant, there is a need for an improved colored composition in which an average of more than two ultraviolet radiation transorber molecules are covalently coupled to each molecule of the molecular includant.
Accordingly, the present invention also relates to a composition which includes a colorant and a functionalized molecular includant. For illustrative purposes only, Examples 12 through 19, and 21 through 22 disclose other methods of preparing and associating colorants and ultraviolet radiation transorbers to cyclodextrins, wherein more than two molecules of the ultraviolet radiation transorber are covalently coupled to each molecule of the molecular includant. Further, Examples 29 and 31 disclose methods of preparing and associating arylketoalkene stabilizers with cyclodextrin, wherein the cyclodextrin has an average of approximately 3 or 4 stabilizer molecules attached thereto.
The present invention also provides a method of making a functionalized molecular includant. The method of making a functionalized molecular includant involves the steps of providing a derivatized ultraviolet radiation transorber having a nucleophilic group, providing a derivatized molecular includant having more than two leaving groups per molecule, and reacting the derivatized ultraviolet radiation transorber with the derivatized molecular includant under conditions sufficient to result in the covalent coupling of an average of more than two ultraviolet radiation transorber molecules to each molecular includant molecule. By way of example, the derivatized ultraviolet radiation transorber may be 2-[p-(2-methyl-2-mercaptomethylpropionyl)phenoxy]ethyl 1,3-dioxo-2-isoindoline-acetate. As another example, the derivatized ultraviolet radiation transorber may be 2-mercaptomethyl-2-methyl-4'-[2-[p-(3-oxobutyl)phenoxy]ethoxy]propiophenone.
In general, the derivatized ultraviolet radiation transorber and the derivatized molecular includant are selected to cause the covalent coupling of the ultraviolet radiation transorber to the molecular includant by means of a bimolecular nucleophilic substitution reaction. Consequently, the choice of the nucleophilic group and the leaving groups and the preparation of the derivatized ultraviolet radiation transorber and derivatized molecular includant, respectively, may be readily accomplished by those having ordinary skill in the art without the need for undue experimentation.
The nucleophilic group of the derivatized ultraviolet radiation transorber may be any nucleophilic group capable of participating in a bimolecular nucleophilic substitution reaction, provided, of course, that the reaction results in the covalent coupling of more than two molecules of the ultraviolet radiation transorber to the molecular includant. The nucleophilic group generally will be a Lewis base, i.e., any group having an unshared pair of electrons. The group may be neutral or negatively charged. Examples of nucleophilic groups include, by way of illustration only, aliphatic hydroxy, aromatic hydroxy, alkoxides, carboxy, carboxylate, amino, and mercapto.
Similarly, the leaving group of the derivatized molecular includant may be any leaving group capable of participating in a bimolecular nucleophilic substitution reaction, again provided that the reaction results in the covalent coupling of more than two molecules of the ultraviolet radiation transorber to the molecular includant. Examples of leaving groups include, also by way of illustration only, p-touenesulfonates (tosylates), p-bromobenzenesulfonates (brosylates), p-nitrobenzenesulfonates (nosylates), methanesulfonates (mesylates), oxonium ions, alkyl perchlorates, ammonioalkane sulfonate esters (betylates), alkyl fluorosulfonates, trifluoromethanesulfonates (triflates), nonafluorobutanesulfonates (nonaflates), and 2,2,2-trifluoroethanesulfonates (tresylates).
The reaction of the derivatized ultraviolet radiation transorber with the derivatized molecular includant is carried out in solution. The choice of solvent depends upon the solubilities of the two derivatized species. As a practical matter, a particularly useful solvent is N,N-dimethylformamide (DMF).
The reaction conditions, such as temperature, reaction time, and the like generally are matters of choice based upon the natures of the nucleophilic and leaving groups. Elevated temperatures usually are not required. For example, the reaction temperature may be in a range of from about 0.degree. C. to around ambient temperature, i.e., to 20.degree.-25.degree. C.
The preparation of the functionalized molecular includant as described above generally is carried out in the absence of the colorant. However, the colorant may be associated with the derivatized molecular includant before reacting the derivatized ultraviolet radiation transorber with the derivatized molecular includant, particularly if a degree of substitution greater than about three is desired. When the degree of substitution is about three, it is believed that the association of the colorant with the functionalized molecular includant still may permit the colorant to be at least partially included in a cavity of the functionalized molecular includant. At higher degrees of substitution, such as about six, steric hindrance may partially or completely prevent the colorant from being at least partially included in a cavity of the functionalized molecular includant. Consequently, the colorant may be associated with the derivatized molecular includant which normally will exhibit little, if any, steric hindrance. In this instance, the colorant will be at least partially included in a cavity of the derivatized molecular includant. The above-described bimolecular nucleophilic substitution reaction then may be carried out to give a colored composition of the present invention in which the colorant is at least partially included in a cavity of the functionalized molecular includant.
Mutable Compositions
As stated above, the present invention provides compositions comprising a colorant which, in the presence of a radiation transorber, is mutable when exposed to a specific wavelength of radiation, while at the same time, provides light stability to the colorant with respect to sunlight and artificial light. Desirably, the mutated colorant will be stable, i.e., not appreciably adversely affected by radiation normally encountered in the environment, such as natural or artificial light and heat. Thus, desirably, a colorant rendered colorless will remain colorless indefinitely.
The dye, for example, may be an organic dye. Organic dye classes include, by way of illustration only, triarylmethyl dyes, such as Malachite Green Carbinol base {4-(dimethylamino)-.alpha.-[4-(dimethylamino)phenyl]-.alpha.-phenylbenzene-methanol}, Malachite Green Carbinol hydrochloride {N-4-[[4-(dimethylamino)phenyl]phenylmethylene]-2,5-cyclohexyldien-1-ylidene]-N-methyl-methanaminium chloride or bis[p-(dimethylamino)phenyl]phenylmethylium chloride}, and Malachite Green oxalate {N-4-[[4-(dimethylamino)phenyl]phenylmethylene]-2,5-cyclohexyldien-1-ylidene]-N-methylmethanaminium chloride or bis [p-(dimethylamino)phenyl]phenylmethylium oxalate}; monoazo dyes, such as Cyanine Black, Chrysoidine [Basic Orange 2; 4-(phenylazo)-1,3-benzenediamine monohydrochloride], Victoria Pure Blue BO, Victoria Pure Blue B, basic fuschin and .beta.-Naphthol Orange; thiazine dyes, such as Methylene Green, zinc chloride double salt [3,7-bis(dimethylamino)-6-nitrophenothiazin-5-ium chloride, zinc chloride double salt]; oxazine dyes, such as Lumichrome (7,8-dimethylalloxazine); naphthalimide dyes, such as Lucifer Yellow CH {6-amino-2-[(hydrazinocarbonyl)amino]-2,3-dihydro-1,3-dioxo-1H-benz[de]isoquinoline-5,8-disulfonic acid dilithium salt}; azine dyes, such as Janus Green B {3-(diethylamino)-7-[[4-(dimethylamino)phenyl]azo]-5-phenylphenazinium chloride}; cyanine dyes, such as Indocyanine Green {Cardio-Green or Fox Green; 2-[7-[1,3-dihydro-1,1-dimethyl-3-(4-sulfobutyl)-2H-benz [e]indol-2-ylidene]-1,3,5-heptatrienyl]-1,1-dimethyl-3-(4-sulfobutyl)-1H-benz[e]indolium hydroxide inner salt sodium salt}; indigo dyes, such as Indigo {Indigo Blue or Vat Blue 1; 2-(1,3-dihydro-3-oxo-2H-indol-2-ylidene)-1,2-dihydro-3H-indol-3-one}; coumarin dyes, such as 7-hydroxy-4-methylcoumarin (4-methylumbelliferone); benzimidazole dyes, such as Hoechst 33258 [bisbenzimide or 2-(4-hydroxyphenyl)-5-(4-methyl-1-piperazinyl) -2,5-bi-1H-benzimidazole trihydrochloride pentahydrate]; paraquinoidal dyes, such as Hematoxylin {Natural Black 1; 7,11b-dihydrobenz[b]indeno[1,2-d]pyran-3,4,6a,9,10(6H)-pentol}; fluorescein dyes, such as Fluoresceinamine (5-aminofluorescein); diazonium salt dyes, such as Diazo Red RC (Azoic Diazo No. 10 or Fast Red RC salt; 2-methoxy-5-chlorobenzenediazonium chloride, zinc chloride double salt); azoic diazo dyes, such as Fast Blue BB salt (Azoic Diazo No. 20; 4-benzoylamino-2,5-diethoxybenzene diazonium chloride, zinc chloride double salt); phenylenediamine dyes, such as Disperse Yellow 9 [N-(2,4-dinitrophenyl)-1,4-phenylenediamine or Solvent Orange 53]; diazo dyes, such as Disperse Orange 13 [Solvent Orange 52; 1-phenylazo-4-(4-hydroxyphenylazo)naphthalene]; anthraquinone dyes, such as Disperse Blue 3 [Celliton Fast Blue FFR; 1-methylamino-4-(2-hydroxyethylamino)-9,10-anthraquinone], Disperse Blue 14 [Celliton Fast Blue B; 1,4-bis(methylamino)-9,10-anthraquinone], and Alizarin Blue Black B (Mordant Black 13); trisazo dyes, such as Direct Blue 71 {Benzo Light Blue FFL or Sirius Light Blue BRR; 3-[(4-[(4-[(6-amino-1-hydroxy-3-sulfo-2-naphthalenyl)azo]-6-sulfo-1-naphthalenyl)azo]-1-naphthalenyl)azo]-1,5-naphthalenyl)azo]1,5-naphthalenedisulfonic acid tetrasodium salt}; xanthene dyes, such as 2,7-dichlorofluorescein; proflavine dyes, such as 3,6-diaminoacridine hemisulfate (Proflavine); sulfonaphthalein dyes, such as Cresol Red (o-cresolsulfonaphthalein); phthalocyanine dyes, such as Copper Phthalocyanine {Pigment Blue 15; (SP-4-1)-[29H, 31H-phthalocyanato(2-)-N.sup.29,N.sup.30,N.sup.31,N.sup.32 ]copper}; carotenoid dyes, such as trans-.beta.-carotene (Food Orange 5); carminic acid dyes, such as Carmine, the aluminum or calcium-aluminum lake of carminic acid (7-a-D-glucopyranosyl-9,10-dihydro-3,5,6,8-tetrahydroxy-1 -methyl-9,10-dioxo-2-anthracenecarbonylic acid); azure dyes, such as Azure A [3-amino-7-(dimethylamino)phenothiazin-5-ium chloride or 7-(dimethylamino)-3-imino-3H-phenothiazine hydrochloride]; and acridine dyes, such as Acridine Orange [Basic Orange 14; 3,8-bis(dimethylamino)acridine hydrochloride, zinc chloride double salt] and Acriflavine (Acriflavine neutral; 3,6-diamino-10-methylacridinium chloride mixture with 3,6-acridinediamine).
The present invention includes unique compounds, namely, radiation transorbers, that are capable of absorbing narrow ultraviolet wavelength radiation, while at the same time, imparting light-stability to a colorant with which the compounds are associated. The compounds are synthesized by combining a wavelength-selective sensitizer and a photoreactor. The photoreactors oftentimes do not efficiently absorb high energy radiation. When combined with the wavelength-selective sensitizer, the resulting compound is a wavelength specific compound that efficiently absorbs a very narrow spectrum of radiation. The wavelength-selective sensitizer may be covalently coupled to the photoreactor.
By way of example, the wavelength-selective sensitizer may be selected from the group consisting of phthaloylglycine and 4-(4-oxyphenyl)-2-butanone. As another example, the photoreactor may be selected from the group consisting of 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one and cyclohexyl-phenyl ketone ester. Other photoreactors are listed by way of example, in the detailed description below regarding the improved stabilized composition of the present invention. As a further example, the ultraviolet radiation transorber may be 2-[p-2-methyllactoyl)phenoxy]ethyl 1,3-dioxo-2-isoin-dolineacetate. As still another example, the ultraviolet radiation transorber may be 2-hydroxy-2-methyl-4'-2-[p-(3-oxobutyl)phenoxy]-propiophenone.
Although the colorant and the ultraviolet radiation transorber have been described as separate compounds, they can be part of the same molecule. For example, they can be covalently coupled to each other, either directly, or indirectly through a relatively small molecule, or spacer. Alternatively, the colorant and ultraviolet radiation transorber can be covalently coupled to a large molecule, such as an oligomer or a polymer. Further, the colorant and ultraviolet radiation transorber may be associated with a large molecule by van der Waals forces, and hydrogen bonding, among other means. Other variations will be readily apparent to those having ordinary skill in the art.
For example, in an embodiment of the composition of the present invention, the composition further comprises a molecular includant. Thus, the cavity in the molecular includant can be a tunnel through the molecular includant or a cave-like space or a dented-in space in the molecular includant. The cavity can be isolated or independent, or connected to one or more other cavities.
The molecular includant can be inorganic or organic in nature. In certain embodiments, the chemical structure of the molecular includant is adapted to form a molecular inclusion complex. Examples of molecular includants are, by way of illustration only, clathrates or intercalates, zeolites, and cyclodextrins. Examples of cyclodextrins include, but are not limited to, .alpha.-cyclodextrin, .beta.-cyclodextrin, .gamma.-cyclodextrin, hydroxypropyl .beta.-cyclodextrin, hydroxyethyl .beta.-cyclodextrin, sulfated .beta.-cyclodextrin, hydroxyethyl .alpha.cyclodextrin, carboxymethyle .alpha. cyclodextrin, carboxymethyl .beta. cyclodextrin, carboxymethyl .gamma. cyclodextrin, octyl succinated .alpha. cyclodextrin, octyl succinated .beta. cyclodextrin, octyl succinated .gamma. cyclodextrin and sulfated .beta. and .gamma.-cyclodextrin (American Maize-Products Company, Hammond, Ind.).
The desired molecular includant is .alpha.-cyclodextrin. More particularly, in some embodiments, the molecular includant is an .alpha.-cyclodextrin. In other embodiments, the molecular includant is a .beta.-cyclodextrin. Although not wanting to be bound by the following theory, it is believed that the closer the transorber molecule is to the mutable colorant on the molecular includant, the more efficient the interaction with the colorant to effect mutation of the colorant. Thus, the molecular includant with functional groups that can react with and bind the transorber molecule and that are close to the binding site of the mutable colorant are the more desirable molecular includants.
In some embodiments, the colorant and the ultraviolet radiation transorber are associated with the molecular includant. The term "associated", in its broadest sense, means that the colorant and the ultraviolet radiation transorber are at least in close proximity to the molecular includant. For example, the colorant and/or the ultraviolet radiation transorber can be maintained in close proximity to the molecular includant by hydrogen bonding, van der Waals forces, or the like. Alternatively, either or both of the colorant and the ultraviolet radiation transorber can be covalently bonded to the molecular includant. In certain embodiments, the colorant will be associated with the molecular includant by means of hydrogen bonding and/or van der Waals forces or the like, while the ultraviolet radiation transorber is covalently bonded to the molecular includant. In other embodiments, the colorant is at least partially included within the cavity of the molecular includant, and the ultraviolet radiation transorber is located outside of the cavity of the molecular includant.
In one embodiment wherein the colorant and the ultraviolet radiation transorber are associated with the molecular includant, the colorant is crystal violet, the ultraviolet radiation transorber is a dehydrated phthaloylglycine-2959, and the molecular includant is .beta.-cyclodextrin. In yet another embodiment wherein the colorant and the ultraviolet radiation transorber are associated with the molecular includant, the colorant is crystal violet, the ultraviolet radiation transorber is 4(4-hydroxyphenyl) butan-2-one-2959 (chloro substituted), and the molecular includant is .beta.-cyclodextrin.
In another embodiment wherein the colorant and the ultraviolet radiation transorber are associated with the molecular includant, the colorant is malachite green, the ultraviolet radiation transorber is IRGACURE.RTM. 184, and the molecular includant is .beta.-cyclodextrin as shown in FIG. 1. In still another embodiment wherein the colorant and the ultraviolet radiation transorber are associated with the molecular includant, the colorant is Victoria Pure Blue BO, the ultraviolet radiation transorber is IRGACURE.RTM. 184, and the molecular includant is .beta.-cyclodextrin as shown in FIG. 2.
The present invention also relates to a method of mutating the colorant in the composition of the present invention. Briefly described, the method comprises irradiating a composition containing a mutable colorant and a radiation transorber with radiation at a dosage level sufficient to mutate the colorant. As stated above, in one embodiment the composition further includes a molecular includant. In another embodiment, the composition is applied to a substrate before being irradiated with ultraviolet radiation. The composition of the present invention may be irradiated with radiation having a wavelength of between about 4 to about 1,000 nanometers. The radiation to which the composition of the present invention is exposed generally will have a wavelength of from about 4 to about 1,000 nanometers. Thus, the radiation may be ultraviolet radiation, including near ultraviolet and far or vacuum ultraviolet radiation; visible radiation; and near infrared radiation. Desirably, the composition is irradiated with radiation having a wavelength of from about 4 to about 700 nanometers. More desirably, the composition of the present invention is irradiated with ultraviolet radiation having a wavelength of from about 4 to about 400 nanometers. It is more desirable that the radiation has a wavelength of between about 100 to 375 nanometers.
Especially desirable radiation is incoherent, pulsed ultraviolet radiation produced by a dielectric barrier discharge lamp. Even more preferably, the dielectric barrier discharge lamp produces radiation having a narrow bandwidth, i.e., the half width is of the order of approximately 5 to 100 nanometers. Desirably, the radiation will have a half width of the order of approximately 5 to 50 nanometers, and more desirably will have a half width of the order of 5 to 25 nanometers. Most desirably, the half width will be of the order of approximately 5 to 15 nanometers.
The amount or dosage level of ultraviolet radiation that the colorant of the present invention is exposed to will generally be that amount which is necessary to mutate the colorant. The amount of ultraviolet radiation necessary to mutate the colorant can be determined by one of ordinary skill in the art using routine experimentation. Power density is the measure of the amount of radiated electromagnetic power traversing a unit area and is usually expressed in watts per centimeter squared (W/cm.sup.2). The power density level range is between approximately 5 mW/cm.sup.2 and 15 mW/cm.sup.2, more particularly 8 to 10 mW/cm.sup.2. The dosage level, in turn, typically is a function of the time of exposure and the intensity or flux of the radiation source which irradiates the colored composition. The latter is affected by the distance of the composition from the source and, depending upon the wavelength range of the ultraviolet radiation, can be affected by the atmosphere between the radiation source and the composition. Accordingly, in some instances it may be appropriate to expose the composition to the radiation in a controlled atmosphere or in a vacuum, although in general neither approach is desired.
With regard to the mutation properties of the present invention, photochemical processes involve the absorption of light quanta, or photons, by a molecule, e.g., the ultraviolet radiation transorber, to produce a highly reactive electronically excited state. However, the photon energy, which is proportional to the wavelength of the radiation, cannot be absorbed by the molecule unless it matches the energy difference between the unexcited, or original, state and an excited state. Consequently, while the wavelength range of the ultraviolet radiation to which the colored composition is exposed is not directly of concern, at least a portion of the radiation must have wavelengths which will provide the necessary energy to raise the ultraviolet radiation transorber to an energy level which is capable of interacting with the colorant.
It follows, then, that the absorption maximum of the ultraviolet radiation transorber ideally will be matched with the wavelength range of the ultraviolet radiation to increase the efficiency of the mutation of the colorant. Such efficiency also will be increased if the wavelength range of the ultraviolet radiation is relatively narrow, with the maximum of the ultraviolet radiation transorber coming within such range. For these reasons, especially suitable ultraviolet radiation has a wavelength of from about 100 to about 375 nanometers. Ultraviolet radiation within this range desirably may be incoherent, pulsed ultraviolet radiation from a dielectric barrier discharge excimer lamp.
The term "incoherent, pulsed ultraviolet radiation" has reference to the radiation produced by a dielectric barrier discharge excimer lamp (referred to hereinafter as "excimer lamp"). Such a lamp is described, for example, by U. Kogelschatz, "Silent discharges for the generation of ultraviolet and vacuum ultraviolet excimer radiation," Pure & Appl. Chem., 62, No. 9, pp. 1667-1674 (1990); and E. Eliasson and U. Kogelschatz, "UV Excimer Radiation from Dielectric-Barrier Discharges," Appl. Phys. B, 46, pp. 299-303 (1988). Excimer lamps were developed originally by ABB Infocom Ltd., Lenzburg, Switzerland. The excimer lamp technology since has been acquired by Haraus Noblelight AG, Hanau, Germany.
The excimer lamp emits radiation having a very narrow bandwidth, i.e., radiation in which the half width is of the order of 5-15 nanometers. This emitted radiation is incoherent and pulsed, the frequency of the pulses being dependent upon the frequency of the alternating current power supply which typically is in the range of from about 20 to about 300 kHz. An excimer lamp typically is identified or referred to by the wavelength at which the maximum intensity of the radiation occurs, which convention is followed throughout this specification. Thus, in comparison with most other commercially useful sources of ultraviolet radiation which typically emit over the entire ultraviolet spectrum and even into the visible region, excimer lamp radiation is substantially monochromatic.
Excimers are unstable molecular complexes which occur only under extreme conditions, such as those temporarily existing in special types of gas discharge. Typical examples are the molecular bonds between two rare gaseous atoms or between a rare gas atom and a halogen atom. Excimer complexes dissociate within less than a microsecond and, while they are dissociating, release their binding energy in the form of ultraviolet radiation. Known excimers, in general, emit in the range of from about 125 to about 360 nanometers, depending upon the excimer gas mixture.
For example, in one embodiment, the colorant of the present invention is mutated by exposure to 222 nanometer excimer lamps. More particularly, the colorant crystal violet is mutated by exposure to 222 nanometer lamps. Even more particularly, the colorant crystal violet is mutated by exposure to 222 nanometer excimer lamps located approximately 5 to 6 centimeters from the colorant, wherein the lamps are arranged in four parallel columns approximately 30 centimeters long. It is to be understood that the arrangement of the lamps is not critical to this aspect of the invention. Accordingly, one or more lamps may be arranged in any configuration and at any distance which results in the colorant mutating upon exposure to the lamp's ultraviolet radiation. One of ordinary skill in the art would be able to determine by routine experimentation which configurations and which distances are appropriate. Also, it is to be understood that different excimer lamps are to be used with different ultraviolet radiation transorbers. The excimer lamp used to mutate a colorant associated with an ultraviolet radiation transorber should produce ultraviolet radiation of a wavelength that is absorbed by the ultraviolet radiation transorber.
In some embodiments, the molar ratio of ultraviolet radiation transorber to colorant generally will be equal to or greater than about 0.5. As a general rule, the more efficient the ultraviolet radiation transorber is in absorbing the ultraviolet radiation and interacting with, i.e., transferring absorbed energy to, the colorant to effect irreversible mutation of the colorant, the lower such ratio can be. Current theories of molecular photo chemistry suggest that the lower limit to such ratio is 0.5, based on the generation of two free radicals per photon. As a practical matter, however, ratios higher than 1 are likely to be required, perhaps as high as about 10. However, the present invention is not bound by any specific molar ratio range. The important feature is that the transorber is present in an amount sufficient to effect mutation of the colorant.
While the mechanism of the interaction of the ultraviolet radiation transorber with the colorant is not totally understood, it is believed that it may interact with the colorant in a variety of ways. For example, the ultraviolet radiation transorber, upon absorbing ultraviolet radiation, may be converted to one or more free radicals which interact with the colorant. Such free radical-generating compounds typically are hindered ketones, some examples of which include, but are not limited to: benzildimethyl ketal (available commercially as IRGACURE.RTM. 651, Ciba-Geigy Corporation, Hawthorne, N.Y.); 1-hydroxycyclohexyl phenyl ketone (IRGACURE.RTM. 500); 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one] (IRGACURE.RTM. 907); 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (IRGACURE.RTM. 369); and 1-hydroxycyclohexyl phenyl ketone (IRGACURE.RTM. 184).
Alternatively, the ultraviolet radiation may initiate an electron transfer or reduction-oxidation reaction between the ultraviolet radiation transorber and the colorant. In this case, the ultraviolet radiation transorber may be, but is not limited to, Michler's ketone (p-dimethylaminophenyl ketone) or benzyl trimethyl stannate. Or, a cationic mechanism may be involved, in which case the ultraviolet radiation transorber can be, for example, bis[4-(diphenylsulphonio)phenyl)] sulfide bis-(hexafluorophosphate) (DEGACURE.RTM. K185, Ciba-Geigy Corporation, Hawthorne, N.Y.); CYRACURE.RTM. UVI-6990 (Ciba-Geigy Corporation), which is a mixture of bis[4-(diphenylsulphonio)phenyl] sulfide bis(hexafluorophosphate) with related monosulphonium hexafluorophosphate salts; and n5-2,4-(cyclopentadienyl)[1,2,3,4,5,6-n-(methylethyl)benzene]-iron(II) hexafluorophosphate (IRGACURE.RTM. 261).
Stabilizing Compositions
With regard to the light stabilizing activity of the present invention, it has been determined that in some embodiments it is necessary to modify a conventional photoreactor to produce the improved light stable composition of the present invention. The simplest form of the improved light stable composition of the present invention includes a colorant admixed with a photoreactor modified as described below. The modified photoreactor may or may not be combined with a wavelength-selective sensitizer. Many conventional photoreactor molecules have a functional group that is alpha to a carbonyl group. The functional group includes, but is not limited to, hydroxyl groups, ether groups, ketone groups, and phenyl groups.
For example, a preferred radiation transorber that can be used in the present invention is designated phthaloylglycine-2959 and is represented by the following formula: ##STR6##
The photoreactor portion of the ultraviolet radiation transorber has a hydroxyl group (shaded portion) alpha to the carbonyl carbon. The above molecule does not light-stabilize a colorant. However, the hydroxyl group can be removed by dehydration (see Example 4 and 5) yielding the following compound: ##STR7## This dehydrated phthaloylglycine-2959 is capable of light-stabilizing a colorant. Thus, it is believed that removal of the functional group alpha to the carbonyl carbon on any photoreactor molecule will impart the light-stabilizing capability to the molecule. While the dehydrated ultraviolet radiation transorber can impart light-stability to a colorant simply by mixing the molecule with the colorant, it has been found that the molecule is much more efficient at stabilizing colorants when it is attached to an includant, such as cyclodextrin, as described herein.
It is to be understood that stabilization of a colorant can be accomplished according to the present invention by utilizing only the modified photoreactor. In other words, a modified photoreactor without a wavelength selective sensitizer may be used to stabilize a colorant. An example of a photoreactor that is modified according to the present invention is IRGACURE.RTM.2959. The unmodified IRGACURE.RTM. 2959 and the dehydrated IRGACURE.RTM. 2959 bare shown below. ##STR8##
Other photoreactors can be modified according to the present invention to provide stabilizers for dyes. These photoreactors include, but are not limited to: 1-Hydroxy-cyclohexyl-phenyl ketone ("HCPK") (IRGACURE.RTM. 184, Ciba-Geigy); .alpha.,.alpha.-dimethoxy-.alpha.-hydroxy acetophenone (DAROCUR.RTM. 1173, Merck); 1-(4-Isopropylphenyl)-2-hydroxy-2-methyl-propan-1-one (DAROCUR.RTM. 1116, Merck); 1-[4-(2-Hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propan-1-one IRGACURE.RTM.2959, Merck); Poly[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] propan-1-one] (ESACURE.RTM. KIP, Fratelli Lamberti); Benzoin (2-Hydroxy-1,2-diphenylethanone) (ESACURE.RTM. BO, Fratelli Lamberti); Benzoin ethyl ether (2-Ethoxy-1,2-diphenylethanone) (DAITOCURE.RTM. EE, Siber Hegner); Benzoin isopropyl ether (2-Isopropoxy-1,2-diphenylethanone) (VICURE.RTM. 30, Stauffer); Benzoin n-butyl ether (2-Butoxy-1,2-diphenylethanone) (ESACURE.RTM. EB1, Fratelli Lamberti); mixture of benzoin butyl ethers (TRIGONAL.RTM. 14, Akzo); Benzoin iso-butyl ether (2-Isobutoxy-1,2-diphenylethanone) (VICURE.RTM. 10, Stauffer); blend of benzoin n-butyl ether and benzoin isobutyl ether (ESACURE.RTM. EB3, ESACURE.RTM. EB4, Fratelli Lamberti); Benzildimethyl ketal (2,2-Dimethoxy-1,2-diphenylethanone) ("BDK") (IRGACURE.RTM. 651, Ciba-Geigy); 2,2-Diethoxy-1,2-diphenylethanone (UVATONE.RTM. 8302, Upjohn); .alpha.,.alpha.-Diethoxyacetophenone (2,2-Diethoxy-1-phenyl-ethanone) ("DEAP", Upjohn), (DEAP, Rahn); and .alpha.,.alpha.-Di-(n-butoxy)-acetophenone (2,2-Dibutoxyl-1-phenyl-ethanone) (UVATONE.RTM. 8301, Upjohn).
It is known to those of ordinary skill in the art that the dehydration by conventional means of the tertiary alcohols that are alpha to the carbonyl groups is difficult. One conventional reaction that can be used to dehydrate the phthaloylglycine-2959 is by reacting the phthaloylglycine-2959 in anhydrous benzene in the presence of p-toluenesulfonic acid. After refluxing the mixture, the final product is isolated. However, the yield of the desired dehydrated alcohol is only about 15 to 20% by this method.
To increase the yield of the desired dehydrated phthaloylglycine-2959, a new reaction was invented. The reaction is summarized as follows: ##STR9##
It is to be understood that the groups on the carbon alpha to the carbonyl group can be groups other than methyl groups such as aryl or heterocyclic groups. The only limitation on these groups are steric limitations. Desirably, the metal salt used in the Nohr-MacDonald elimination reaction is ZnCl.sub.2. It is to be understood that other transition metal salts can be used in performing the Nohr-MacDonald elimination reaction but ZnCl.sub.2 is the preferred metal salt. The amount of metal salt used in the Nohr-MacDonald elimination reaction is preferably approximately equimolar to the tertiary alcohol compound, such as the photoreactor. The concentration of tertiary alcohol in the reaction solution is between approximately 4% and 50% w/v.
Thus, the stabilizing composition produced by the process of dehydrating a tertiary alcohol that is alpha to a carbonyl group on a photoreactor is shown in the following general formula: ##STR10## wherein R.sub.1 is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;
R.sub.2 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;
R.sub.3 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group; and
R.sub.4 is an aryl, heteroaryl, or substituted aryl group.
Another requirement of the reaction is that it be run in a non-aqueous, non-polar solvent. The preferred solvents for running the Nohr-MacDonald elimination reaction are aromatic hydrocarbons including, but not limited to, xylene, benzene, toluene, cumene, mesitylene, p-cymene, butylbenzene, styrene, and divinylbenzene. It is to be understood that other substituted aromatic hydrocarbons can be used as solvents in the present invention. p-Xylene is the preferred aromatic hydrocarbon solvent, but other isomers of xylene can be used in performing the Nohr-MacDonald elimination reaction.
An important requirement in performing the Nohr-MacDonald elimination reaction is that the reaction be run at a relatively high temperature. The reaction is desirably performed at a temperature of between approximately 80.degree. C. and 150.degree. C. A suitable temperature for dehydrating phthaloylglycine-2959 is approximately 124.degree. C. The time the reaction runs is not critical. The reaction should be run between approximately 30 minutes to 4 hours. However, depending upon the reactants and the solvent used, the timing may vary to achieve the desired yield of product.
It is to be understood that the dehydrated phthaloylglycine-2959 can be attached to the molecular includant in a variety of ways. In one embodiment, the dehydrated phthaloylglycine-2959 is covalently attached to the cyclodextrin as shown in the following structure: ##STR11##
In another embodiment, as shown below, only the modified IRGACURE.RTM. 2959 without the phthaloyl glycine attached is reacted with the cyclodextrin to yield the following compound. This compound is capable of stabilizing a dye that is associated with the molecular includant. It is to be understood that photoreactors other than IRGACURE.RTM. 2959 can be used in the present invention. ##STR12##
In yet another embodiment, the dehydrated phthaloylglycine-2959 can be attached to the molecular includant via the opposite end of the molecule. One example of this embodiment is shown in the following formula: ##STR13##
Another stabilizer that is considered part of the present invention is an arylketoalkene having the following general formula: ##STR14## wherein if R.sub.1 is an aryl group, then R.sub.2 is a hydrogen; heterocyclic; alkyl; aryl, or a phenyl group, the phenyl group optionally being substituted with an alkyl, halo, amino, or a thiol group; and if R.sub.2 is an aryl group, then R.sub.1 is hydrogen; heterocyclic; alkyl; aryl, or a phenyl group, the phenyl group optionally being substituted with an alkyl, halo, amino, or a thiol group. Preferably, the alkene group is in the trans configuration although it can be in the cis configuration.
Desirably, the arylketoalkene stabilizing compound has the following formula: ##STR15##
The arylketoalkene may also function as a wavelength-specific sensitizer in the present invention, and it may be associated with any of the previously discussed photoreactors. One method of associating a photoreactor with the arylketoalkene compound of the present invention is described in Example 32. The arylketoalkene compound may optionally be covalently bonded to the reactive species-generating photoinitiator. It is to be understood that the arylketoalkene compound of the present invention is not to be used with photoreactors in a composition where stability in natural sunlight is desired. More particularly, as the arylketoalkene compounds absorb radiation in the range of about 270 to 310 depending on the identity of R.sub.1 and R.sub.2, then these compounds are capable of absorbing the appropriate radiation from sunlight. Accordingly, these compounds when admixed with a photoreactor can effect a mutation of the colorant upon exposure to sunlight. Where such a change in color is not desired, then a photoreactor is not to be admixed with the arylketoalkene compound of the present invention, and the arylketoalkene compound is to be used with a colorant without a photoreactor.
In the embodiment where the arylketoalkene compound is covalently attached to another molecule, whichever R.sub.1 or R.sub.2 that is an aryl group will have a group including, but not limited to, a carboxylic acid group, an aldehyde group, an amino group, a haloalkyl group, a hydroxyl group, or a thioalkyl group attached thereto to allow the arylketoalkene to be covalently bonded to the other molecule. Accordingly, the arylketoalkene stabilizing compound is represented by the following formula: ##STR16##
Although it is preferred that the group attached to the aryl group is para to the remainder of the stabilizer molecule, the group may also be ortho or meta to the remainder of the molecule.
It is to be understood that the arylketoalkene stabilizing compound can be an extended conjugated bond system arylketoalkene compound. In this embodiment, R.sub.1, or R.sub.2, or both R.sub.1 and R.sub.2, in the above general formula are phenyl groups substituted with one or more groups that extend the area of conjugation of the delocalized, pi electrons. More particularly, R.sub.1, or R.sub.2, or both R.sub.1 and R.sub.2, are phenyl groups substituted with one or more carbonyl, ethylene, phenyl, ester, aryl, substituted aryl, or vinylic groups, wherein the groups are sequentially arranged such that only one of the groups is directly attached to the phenyl group, and the other groups are bonded to that attached group thereby extending the conjugation of the compound by forming a chain of unsaturated groups. It is to be understood that the extended conjugated compound of the present invention includes any combination of the above groups, and any number of the above groups.
A desirable extended conjugated arylketoalkene stabilizing compound of the present invention has the following formula: ##STR17##
Another desirable arylketoalkene stabilizing compound has the following formula: ##STR18##
The extended stabilizing compounds of the present invention may be produced by any method known to one of ordinary skill in the art. For example, one method is described in Examples 38 and 39 which utilizes an intermediate molecule having the following formula: ##STR19##
It is to be understood that the hydroxy group on the phenyl group of the above intermediate may be substituted with any other group that will provide a linkage between the molecules shown in Examples 38 and 39 such that the product will have an extended conjugated bond system. The resultant linkage between the molecules produced in Examples 38 and 39 is an ester linkage (--O--(C.dbd.O)--). However, the linkage may include, but is not limited to, a ketone linkage (--(C.dbd.O)--), an ether linkage (--O--), a sulfide linkage (--S--), an amino linkage (--NH--), or an amide linkage. A desirable linkage is an ester linkage.
A desirable arylketoalkene stabilizing compound with a ketone linkage has the following formula: ##STR20##
Yet another desirable arylketoalkene stabilizing compound with a ketone linkage has the following formula: ##STR21##
The extended conjugated arylketoalkene stabilizing compound of the present invention is not limited to only two of the compounds shown in Examples 38 and 39 linked together. It is to be understood that the extended conjugated compound may include a multiplicity of the compounds shown in Examples 38 and 39 linked together.
The extended conjugated arylketoalkene stabilizing compound of the present invention is extremely stable. Although not wanting to be limited by the following, it is believed that the above extended conjugated compounds are low triplet state energy species, and are yellow in color. As the chain of conjugation is extended, it is believed that the color shifts to red or orange.
Accordingly, this embodiment of the present invention provides a stabilizing arylketoalkene which, when associated with a colorant, stabilizes the colorant. Therefore, the above arylketoalkene can be used as an additive to any colorant composition. For example, as the arylketoalkene compound is not water soluble, it can be directly added to solvent or oil colorant compositions. Additionally, the arylketoalkene compound can be added to other colorant compositions that contain additives enabling the solubilization of the compound therein.
Further, the arylketoalkene stabilizing compounds can be solubilized in aqueous solution by a variety of means. One means of solubilizing the arylketoalkene stabilizing compound of the present invention is to attach the compound to a large water soluble molecule, such as a cyclodextrin, as described in Examples 28 through 31, and Examples 40 and 41. Desirably, between about 1 and 12 arylketoalkene molecules can be attached to a cyclodextrin molecule. More desirably, between about 4 to about 9 arylketoalkene molecules are attached to a cyclodextrin molecule. Accordingly, the arylketoalkene compound attached to cyclodextrin can be added to any aqueous colorant system to stabilize the colorant therein. It is to be understood that the stabilizing arylketoalkenes do not have to be attached to the molecular includants to exhibit their stabilizing activity.
Therefore, this embodiment provides a method for stabilizing colorant compositions by admixing the aryketoalkene compound with the colorant composition in an amount effective to stabilize the composition. The arylketoalkenes desirably should be present in the colorant medium or solution at a concentration of approximately 0.1 to 50% by weight, desirably between approximately 20% and 30% by weight. If no cyclodextrin is used, the desirable range is approximately 1 part dye to approximately 20 parts arylketoalkene.
Although the arylketoalkene compound need only be associated with the colorant, in some embodiments of the present invention, the arylketoalkene compound may be covalently bonded to the colorant.
Although not wanting to be limited by the following, it is theorized that the arylketoalkene compound of the present invention stabilizes colorants through functioning as a singlet oxygen scavenger. In the alternative, it is theorized that the arylketoalkene compound functions as a stabilizer of a colorant via the resonance of the unshared electron pairs in the p orbitals, e.g., it functions as an energy sink.
As a practical matter, the colorant, ultraviolet radiation transorber, modified photoreactor, arylketoalkene stabilizer, and molecular includant are likely to be solids depending upon the constituents used to prepare the molecules. However, any or all of such materials can be a liquid. The colored composition can be a liquid either because one or more of its components is a liquid, or, when the molecular includant is organic in nature, a solvent is employed. Suitable solvents include, but are not limited to, amides, such as N,N-dimethylformamide; sulfoxides, such as dimethylsulfoxide; ketones, such as acetone, methyl ethyl ketone, and methyl butyl ketone; aliphatic and aromatic hydrocarbons, such as hexane, octane, benzene, toluene, and the xylenes; esters, such as ethyl acetate; water; and the like. When the molecular includant is a cyclodextrin, particularly suitable solvents are the amides and sulfoxides.
In an embodiment where the composition of the present invention is a solid, the effectiveness of the above compounds on the colorant is improved when the colorant and the selected compounds are in intimate contact. To this end, the thorough blending of the components, along with other components which may be present, is desirable. Such blending generally is accomplished by any of the means known to those having ordinary skill in the art. When the colored composition includes a polymer, blending is facilitated if the colorant and the ultraviolet radiation transorber are at least partly soluble in softened or molten polymer. In such case, the composition is readily prepared in, for example, a two-roll mill. Alternatively, the composition of the present invention can be a liquid because one or more of its components is a liquid.
For some applications, the composition of the present invention typically will be utilized in particulate form. In other applications, the particles of the composition should be very small. Methods of forming such particles are well known to those having ordinary skill in the art.
The colored composition of the present invention can be utilized on or in any substrate. If one desires to mutate the colored composition that is present in a substrate, however, the substrate should be substantially transparent to the ultraviolet radiation which is employed to mutate the colorant. That is, the ultraviolet radiation will not significantly interact with or be absorbed by the substrate. As a practical matter, the composition typically will be placed on a substrate, with the most common substrate being paper. Other substrates, including, but not limited to, woven and nonwoven webs or fabrics, films, and the like, can be used, however.
The colored composition optionally may also contain a carrier, the nature of which is well known to those having ordinary skill in the art. For many applications, the carrier will be a polymer, typically a thermosetting or thermoplastic polymer, with the latter being the more common.
Further examples of thermoplastic polymers include, but are not limited to: end-capped polyacetals, such as poly(oxymethylene) or polyformaldehyde, poly(trichloroacetaldehyde), poly(n-valeraldehyde), poly(acetaldehyde), poly(propionaldehyde), and the like; acrylic polymers, such as polyacrylamide, poly(acrylic acid), poly(methacrylic acid), poly(ethyl acrylate), poly(methyl methacrylate), and the like; fluorocarbon polymers, such as poly(tetrafluoroethylene), perfluorinated ethylenepropylene copolymers, ethylenetetrafluoroethylene copolymers, poly-(chlorotrifluoroethylene), ethylene-chlorotrifluoroethylene copolymers, poly(vinylidene fluoride), poly(vinyl fluoride), and the like; epoxy resins, such as the condensation products of epichlorohydrin and bisphenol A; polyamides, such as poly(6-aminocaproic acid) or poly(.epsilon.-caprolactam), poly(hexamethylene adipamide), poly(hexamethylene sebacamide), poly(11-aminoundecanoic acid), and the like; polyaramides, such as poly(imino-1,3-phenyleneiminoisophthaloyl) or poly(m-phenylene isophthalamide), and the like; parylenes, such as poly-p-xylylene, poly(chloro-p-xylene), and the like; polyaryl ethers, such as poly(oxy-2,6-dimethyl-1,4-phenylene) or poly(p-phenylene oxide), and the like; polyaryl sulfones, such as poly(oxy-1,4-phenylenesulfonyl-1,4phenyleneoxy-1,4-phenylene-isopropylidene-1,4-phenylene), poly(sulfonyl-1,4-phenyleneoxy-1,4-phenylenesulfonyl-4,4-biphenylene), and the like; polycarbonates, such as poly(bisphenol A) or poly(carbonyldioxy-1,4-phenyleneisopropylidene-1,4-phenylene), and the like; polyesters, such as poly(ethylene terephthalate), poly(tetramethylene terephthalate), poly(cyclohexylene-1,4-dimethylene terephthalate) or poly(oxymethylene-1,4-cyclohexylenemethyleneoxyterephthaloyl), and the like; polyaryl sulfides, such as poly(p-phenylene sulfide) or poly(thio-1,4-5 phenylene), and the like; polyimides, such as poly-(pyromellitimido-1,4-phenylene), and the like; polyolefins, such as polyethylene, polypropylene, poly(1-butene), poly(2-butene), poly(1-pentene), poly(2-pentene), poly(3-methyl-1-pentene), poly(4-methyl-1-pentene), 1,2-poly-1,3-butadiene, 1,4-poly-1,3-butadiene, polyisoprene, polychloroprene, polyacrylonitrile, poly(vinyl acetate), poly(vinylidene chloride), polystyrene, and the like; and copolymers of the foregoing, such as acrylonitrile-butadienestyrene (ABS) copolymers, styrene-n-butylmethacrylate copolymers, ethylene-vinyl acetate copolymers, and the like.
Some of the more commonly used thermoplastic polymers include styrene-n-butyl methacrylate copolymers, polystyrene, styrene-n-butyl acrylate copolymers, styrene-butadiene copolymers, polycarbonates, poly(methyl methacrylate), poly(vinylidene fluoride), polyamides (nylon-12), polyethylene, polypropylene, ethylene-vinyl acetate copolymers, and epoxy resins.
Examples of thermosetting polymers include, but are not limited to, alkyd resins, such as phthalic anhydride-glycerol resins, maleic acid-glycerol resins, adipic acid-glycerol resins, and phthalic anhydride-pentaerythritol resins; allylic resins, in which such monomers as diallyl phthalate, diallyl isophthalate diallyl maleate, and diallyl chlorendate serve as nonvolatile cross-linking agents in polyester compounds; amino resins, such as aniline-formaldehyde resins, ethylene urea-formaldehyde resins, dicyandiamide-formaldehyde resins, melamine-formaldehyde resins, sulfonamide-formaldehyde resins, and urea-formaldehyde resins; epoxy resins, such as cross-linked epichlorohydrin-bisphenol A resins; phenolic resins, such as phenol-formaldehyde resins, including Novolacs and resols; and thermosetting polyesters, silicones, and urethanes.
In addition to the colorant, and ultraviolet radiation transorber or functionalized molecular includant, modified photoreactor, arylketoalkene stabilizer, and optional carrier, the colored composition of the present invention also can contain additional components, depending upon the application for which it is intended. Examples of such additional components include, but are not limited to, charge carriers, stabilizers against thermal oxidation, viscoelastic properties modifiers, cross-linking agents, plasticizers, charge control additives such as a quaternary ammonium salt; flow control additives such as hydrophobic silica, zinc stearate, calcium stearate, lithium stearate, polyvinylstearate, and polyethylene powders; and fillers such as calcium carbonate, clay and talc, among other additives used by those having ordinary skill in the art. Charge carriers are well known to those having ordinary skill in the art and typically are polymer-coated metal particles. The identities and amounts of such additional components in the colored composition are well known to one of ordinary skill in the art.
The present invention is further described by the examples which follow. Such examples, however, are not to be construed as limiting in any way either the spirit or scope of the present invention. In the examples, all parts are parts by weight unless stated otherwise.
EXAMPLE 1
This example describes the preparation of a .beta.-cyclodextrin molecular includant having (1) an ultraviolet radiation transorber covalently bonded to the cyclodextrin outside of the cavity of the cyclodextrin, and (2) a colorant associated with the cyclodextrin by means of hydrogen bonds and/or van der Waals forces.
A. Friedel-Crafts Acylation of Transorber
A 250-ml, three-necked, round-bottomed reaction flask was fitted with a condenser and a pressure-equalizing addition funnel equipped with a nitrogen inlet tube. A magnetic stirring bar was placed in the flask. While being flushed with nitrogen, the flask was charged with 10 g (0.05 mole) of 1-hydroxycyclohexyl phenyl ketone (IRGACURE.RTM. 184, Ciba-Geigy Corporation, Hawthorne, N.Y.), 100 ml of anhydrous tetrahydofuran (Aldrich Chemical Company, Inc., Milwaukee, Wis.), and 5 g (0.05 mole) of succinic anhydride (Aldrich Chemical Co., Milwaukee, Wis.). To the continuously stirred contents of the flask then was added 6.7 g of anhydrous aluminum chloride (Aldrich Chemical Co., Milwaukee, Wis.). The resulting reaction mixture was maintained at about 0.degree. C. in an ice bath for about one hour, after which the mixture was allowed to warm to ambient temperature for two hours. The reaction mixture then was poured into a mixture of 500 ml of ice water and 100 ml of diethyl ether. The ether layer was removed after the addition of a small amount of sodium chloride to the aqueous phase to aid phase separation. The ether layer was dried over anhydrous magnesium sulfate. The ether was removed under reduced pressure, leaving 12.7 g (87 percent) of a white crystalline powder. The material was shown to be 1-hydroxycyclohexyl 4-(2-carboxyethyl)carbonylphenyl ketone by nuclear magnetic resonance analysis.
B. Preparation of Acylated Transorber Acid Chloride
A 250-ml round-bottomed flask fitted with a condenser was charged with 12.0 g of 1-hydroxycyclohexyl 4-(2-carboxyethyl)carbonylphenyl ketone (0.04 mole), 5.95 g (0.05 mole) of thionyl chloride (Aldrich Chemical Co., Milwaukee, Wis.), and 50 ml of diethyl ether. The resulting reaction mixture was stirred at 30.degree. C. for 30 minutes, after which time the solvent was removed under reduced pressure. The residue, a white solid, was maintained at 0.01 Torr for 30 minutes to remove residual solvent and excess thionyl chloride, leaving 12.1 g (94 percent) of 1-hydroxycyclohexyl 4-(2-chloroformylethyl)carbonylphenyl ketone.
C. Covalent Bonding of Acylated Transorber to Cyclodextrin
A 250-ml, three-necked, round-bottomed reaction flask containing a magnetic stirring bar and fitted with a thermometer, condenser, and pressure-equalizing addition funnel equipped with a nitrogen inlet tube was charged with 10 g (9.8 mmole) of .beta.-cyclodextrin (American Maize-Products Company, Hammond, Ind.), 31.6 g (98 mmoles) of 1-hydroxycyclohexyl 4-(2-chloroformylethyl)carbonylphenyl ketone, and 100 ml of N,N-dimethylformamide while being continuously flushed with nitrogen. The reaction mixture was heated to 50.degree. C. and 0.5 ml of triethylamine added. The reaction mixture was maintained at 50.degree. C. for an hour and allowed to cool to ambient temperature. In this preparation, no attempt was made to isolate the product, a .beta.-cyclodextrin to which an ultraviolet radiation transorber had been covalently coupled (referred to hereinafter for convenience as .beta.-cyclodextrin-transorber).
The foregoing procedure was repeated to isolate the product of the reaction. At the conclusion of the procedure as described, the reaction mixture was concentrated in a rotary evaporator to roughly 10 percent of the original volume. The residue was poured into ice water to which sodium chloride then was added to force the product out of solution. The resulting precipitate was isolated by filtration and washed with diethyl ether. The solid was dried under reduced pressure to give 24.8 g of a white powder. In a third preparation, the residue remaining in the rotary evaporator was placed on top of an approximately 7.5-cm column containing about 15 g of silica gel. The residue was eluted with N,N-dimethylformamide, with the eluant being monitored by means of Whatman.RTM. Flexible-Backed TLC Plates (Catalog No. 05-713-161, Fisher Scientific, Pittsburgh, Pa.). The eluted product was isolated by evaporating the solvent. The structure of the product was verified by nuclear magnetic resonance analysis.
D. Association of Colorant with Cyclodextrin-Transorber-Preparation of Colored Composition
To a solution of 10 g (estimated to be about 3.6 mmole) of .beta.-cyclodextrin-transorber in 150 ml of N,N-dimethylformamide in a 250-ml round-bottomed flask was added at ambient temperature 1.2 g (3.6 mmole) of Malachite Green oxalate (Aldrich Chemical Company, Inc., Milwaukee, Wis.), referred to hereinafter as Colorant A for convenience. The reaction mixture was stirred with a magnetic stirring bar for one hour at ambient temperature. Most of the solvent then was removed in a rotary evaporator and the residue was eluted from a silica gel column as already described. The .beta.-cyclodextrin-transorber Colorant A inclusion complex moved down the column first, cleanly separating from both free Colorant A and .beta.-cyclodextrin-transorber. The eluant containing the complex was collected and the solvent removed in a rotary evaporator. The residue was subjected to a reduced pressure of 0.01 Torr to remove residual solvent to yield a blue-green powder.
E. Mutation of Colored Composition
The .beta.-cyclodextrin-transorber Colorant A inclusion complex was exposed to ultraviolet radiation from two different lamps, Lamps A and B. Lamp A was a 222-nanometer excimer lamp assembly organized in banks of four cylindrical lamps having a length of about 30 cm. The lamps were cooled by circulating water through a centrally located or inner tube of the lamp and, as a consequence, they operated at a relatively low temperature, i.e., about 50.degree. C. The power density at the lamp's outer surface typically is in the range of from about 4 to about 20 joules per square meter (J/m.sup.2). However, such range in reality merely reflects the capabilities of current excimer lamp power supplies; in the future, higher power densities may be practical. The distance from the lamp to the sample being irradiated was 4.5 cm. Lamp B was a 500-watt Hanovia medium pressure mercury lamp (Hanovia Lamp Co., Newark, N.J.). The distance from Lamp B to the sample being irradiated was about 15 cm.
A few drops of an N,N-dimethylformamide solution of the .beta.-cyclodextrin-transorber Colorant A inclusion complex were placed on a TLC plate and in a small polyethylene weighing pan. Both samples were exposed to Lamp A and were decolorized (mutated to a colorless state) in 15-20 seconds. Similar results were obtained with Lamp B in 30 seconds.
A first control sample consisting of a solution of Colorant A and .beta.-cyclodextrin in N,N-dimethylformnamide was not decolorized by Lamp A. A second control sample consisting of Colorant A and 1-hydroxycyclohexyl phenyl ketone in N,N-dimethylformamide was decolorized by Lamp A within 60 seconds. On standing, however, the color began to reappear within an hour.
To evaluate the effect of solvent on decolorization, 50 mg of the .beta.-cyclodextrin-transorber Colorant A inclusion complex was dissolved in 1 ml of solvent. The resulting solution or mixture was placed on a glass microscope slide and exposed to Lamp A for 1 minute. The rate of decolorization, i.e., the time to render the sample colorless, was directly proportional to the solubility of the complex in the solvent, as summarized below.
TABLE 1______________________________________ DecolorizationSolvent Solubility Time______________________________________N,N-Dimethylformamide Poor 1 minuteDimethylsulfoxide Soluble <10 secondsAcetone Soluble <10 secondsHexane Insoluble --Ethyl Acetate Poor 1 minute______________________________________
Finally, 10 mg of the .beta.-cyclodextrin-transorber Colorant A inclusion complex were placed on a glass microscope slide and crushed with a pestle. The resulting powder was exposed to Lamp A for 10 seconds. The powder turned colorless. Similar results were obtained with Lamp B, but at a slower rate.
EXAMPLE 2
Because of the possibility in the preparation of the colored composition described in the following examples for the acylated transorber acid chloride to at least partially occupy the cavity of the cyclodextrin, to the partial or complete exclusion of colorant, a modified preparative procedure was carried out. Thus, this example describes the preparation of a .beta.-cyclodextrin molecular includant having (1) a colorant at least partially included within the cavity of the cyclodextrin and associated therewith by means of hydrogen bonds and/or van der Waals forces, and (2) an ultraviolet radiation transorber covalently bonded to the cyclodextrin substantially outside of the cavity of the cyclodextrin.
A. Association of Colorant with a Cyclodextrin
To a solution of 10.0 g (9.8 mmole) of .beta.-cyclodextrin in 150 ml of N,N-dimethylformamide was added 3.24 g (9.6 mmoles) of Colorant A. The resulting solution was stirred at ambient temperature for one hour. The reaction solution was concentrated under reduced pressure in a rotary evaporator to a volume about one-tenth of the original volume. The residue was passed over a silica gel column as described in Part C of Example 1. The solvent in the eluant was removed under reduced pressure in a rotary evaporator to give 12.4 g of a blue-green powder, .beta.-cyclodextrin Colorant A inclusion complex.
B. Covalent Bonding of Acylated Transorber to Cyclodextrin Colorant Inclusion Complex--Preparation of Colored Composition
A 250-ml, three-necked, round-bottomed reaction flask containing a magnetic stirring bar and fitted with a thermometer, condenser, and pressure-equalizing addition funnel equipped with a nitrogen inlet tube was charged with 10 g (9.6 mmole) of .beta.-cyclodextrin Colorant A inclusion complex, 31.6 g (98 mmoles) of 1-hydroxycyclohexyl 4-(2-chloroformylethyl)carbonylphenyl ketone prepared as described in Part B of Example 1, and 150 ml of N,N-dimethylformamide while being continuously flushed with nitrogen. The reaction mixture was heated to 50.degree. C. and 0.5 ml of triethylamine added. The reaction mixture was maintained at 50.degree. C. for an hour and allowed to cool to ambient temperature. The reaction mixture then was worked up as described in Part A, above, to give 14.2 g of .beta.-cyclodextrin-transorber Colorant A inclusion complex, a blue-green powder.
C. Mutation of Colored Composition
The procedures described in Part E of Example 1 were repeated with the .beta.-cyclodextrin-transorber Colorant A inclusion complex prepared in Part B, above, with essentially the same results.
EXAMPLE 3
This example describes a method of preparing an ultraviolet radiation transorber, 2-[p-(2-methyllactoyl)phenoxy]ethyl 1,3-dioxo-2-isoindolineacetate, designated phthaloylglycine-2959.
The following was admixed in a 250 ml, three-necked, round bottomed flask fitted with a Dean & Stark adapter with condenser and two glass stoppers: 20.5 g (0.1 mole) of the wavelength selective sensitizer, phthaloylglycine (Aldrich Chemical Co., Milwaukee, Wis.); 24.6 g (0.1 mole) of the photoreactor, IRGACURE.RTM. 2959 (Ciba-Geigy, Hawthorne, N.Y.); 100 ml of benzene (Aldrich Chemical Co., Milwaukee, Wis.); and 0.4 g p-toluenesulfonic acid (Aldrich Chemical Co., Milwaukee, Wis.). The mixture was heated at reflux for 3 hours after which time 1.8 ml of water was collected. The solvent was removed under reduced pressure to give 43.1 g of white powder. The powder was recrystallized from 30% ethyl acetate in hexane (Fisher) to yield 40.2 g (93%) of a white crystalline powder having a melting point of 153-4.degree. C. The reaction is summarized as follows: ##STR22##
The resulting product, designated phthaloylglycine-2959, had the following physical parameters:
IR [NUJOL MULL] .nu..sub.max 3440, 1760, 1740, 1680, 1600 cm-1
1H NMR [CDCl3] .delta. ppm 1.64[s], 4.25[m], 4.49[m], 6.92[m], 7.25[m], 7.86[m], 7.98[m], 8.06[m] ppm.
EXAMPLE 4
This example describes a method of dehydrating the phthaloylglycine-2959 produced in Example 3.
The following was admixed in a 250 ml round bottomed flask fitted with a Dean & Stark adapter with condenser: 21.6 g (0.05 mole) phthaloylglycine-2959; 100 ml of anhydrous benzene (Aldrich Chemical Co., Milwaukee, Wis.); and 0.1 g p-toluenesulfonic acid (Aldrich Chemical Co., Milwaukee, Wis.). The mixture was refluxed for 3 hours. After 0.7 ml of water had been collected in the trap, the solution was then removed under vacuum to yield 20.1 g (97%) of a white solid. However, analysis of the white solid showed that this reaction yielded only 15 to 20% of the desired deydration product. The reaction is summarized as follows: ##STR23##
The resulting reaction product had the following physical parameters:
IR (NUJOL) .nu..sub.max 1617 cm-1(C.dbd.C--C.dbd.O).
EXAMPLE 5
This example describes the Nohr-MacDonald elimination reaction used to dehydrate the phthaloylglycine-2959 produced in Example 3.
Into a 500 ml round bottomed flask were placed a stirring magnet, 20.0 g (0.048 mole) of the phthaloylglycine-2959, and 6.6 g (0.048 mole) of anhydrous zinc chloride (Aldrich Chemical Co., Milwaukee, Wis.). 250 ml of anhydrous p-xylene (Aldrich Chemical Co., Milwaukee, Wis.) was added and the mixture refluxed under argon atmosphere for two hours. The reaction mixture was then cooled, resulting in a white precipitate which was collected. The white powder was then recrystallized from 20% ethyl acetate in hexane to yield 18.1 g (95%) of a white powder. The reaction is summarized as follows: ##STR24##
The resulting reaction product had the following physical parameters:
Melting Point: 138.degree. C. to 140.degree. C.
Mass spectrum: m/e: 393 M+, 352, 326, 232, 160.
IR (KB) .nu..sub.max 1758, 1708, 1677, 1600 cm-1
1H NMR [DMSO] .delta. ppm 1.8(s), 2.6(s), 2.8 (d), 3.8 (d), 4.6 (m), 4.8 (m), 7.3(m), 7.4 (m), 8.3 (m), and 8.6 (d)
13C NMR [DMSO] .delta. ppm 65.9 (CH2.dbd.).
EXAMPLE 6
This example describes a method of producing a .beta.-cyclodextrin having dehydrated phthaloylglycine-2959 groups from Example 4 or 5 covalently bonded thereto.
The following was admixed in a 100 ml round-bottomed flask: 5.0 g (4 mmole) .beta.-cyclodextrin (American Maize Product Company, Hammond, Ind.) (designated .beta.-CD in the following reaction); 8.3 g (20 mmole) dehydrated phthaloylglycine-2959; 50 ml of anhydrous DMF; 20 ml of benzene; and 0.01 g p-tolulenesulfonyl chloride (Aldrich Chemical Co., Milwaukee, Wis.). The mixture was chilled in a salt/ice bath and stirred for 24 hours. The reaction mixture was poured into 150 ml of weak sodium bicarbonate solution and extracted three times with 50 ml ethyl ether. The aqueous layer was then filtered to yield a white solid comprising the .beta.-cyclodextrin with phthaloylglycine-2959 group attached. A yield of 9.4 g was obtained. Reverse phase TLC plate using a 50:50 DMF:acetonitrile mixture showed a new product peak compared to the starting materials. ##STR25##
The .beta.-cyclodextrin molecule has several primary alcohols and secondary alcohols with which the phthaloylglycine-2959 can react. The above representative reaction only shows a single phthaloylglycine-2959 molecule for illustrative purposes.
EXAMPLE 7
This example describes a method of associating a colorant and an ultraviolet radiation transorber with a molecular includant. More particularly, this example describes a method of associating the colorant crystal violet with the molecular includant .beta.-cyclodextrin covalently bonded to the ultraviolet radiation transorber dehydrated phthaloylglycine-2959 of Example 6.
The following was placed in a 100 ml beaker: 4.0 g .beta.-cyclodextrin having a dehydrated phthaloylglycine-2959 group; and 50 ml of water. The water was heated to 70.degree. C. at which point the solution became clear. Next, 0.9 g (2.4 mmole) crystal violet (Aldrich Chemical Company, Milwaukee, Wis.) was added to the solution, and the solution was stirred for 20 minutes. Next, the solution was then filtered. The filtrand was washed with the filtrate and then dried in a vacuum oven at 84.degree. C. A violet-blue powder was obtained having 4.1 g (92%) yield. The resulting reaction product had the following physical parameters:
U.V. Spectrum DMF .nu..sub.max 610 nm (cf cv .nu..sub.max 604 nm).
EXAMPLE 8
This example describes a method of producing the ultraviolet radiation transorber 4(4-hydroxyphenyl) butan-2-one-2959 (chloro substituted).
The following was admixed in a 250 ml round-bottomed flask fitted with a condenser and magnetic stir bar: 17.6 g (0.1 mole) of the wavelength selective sensitizer, 4(4-hydroxyphenyl) butan-2-one (Aldrich Chemical Company, Milwaukee, Wis.); 26.4 g (0.1 mole) of the photoreactor, chloro substituted IRGACURE.RTM. 2959 (Ciba-Geigy Corporation, Hawthorne, N.Y.); 1.0 ml of pyridine (Aldrich Chemical Company, Milwaukee, Wis.); and 100 ml of anhydrous tetrahydrofuran (Aldrich Chemical Company, Milwaukee, Wis.). The mixture was refluxed for 3 hours and the solvent partially removed under reduced pressure (60% taken off). The reaction mixture was then poured into ice water and extracted with two 50 ml aliquots of diethyl ether. After drying over anhydrous magnesium sulfate and removal of solvent, 39.1 g of white solvent remained. Recrystallization of the powder from 30% ethyl acetate in hexane gave 36.7 g (91%) of a white crystalline powder, having a melting point of 142-3.degree. C. The reaction is summarized in the following reaction: ##STR26##
The resulting reaction product had the following physical parameters:
IR [NUJOL MULL] .nu..sub.max 3460, 1760, 1700, 1620, 1600 cm-1
1H [CDCl3] .delta. ppm 1.62[s], 4.2[m], 4.5[m], 6.9[m] ppm.
The ultraviolet radiation transorber produced in this example, 4(4-hydroxyphenyl) butan-2-one-2959 (chloro substituted), may be associated with .beta.-cyclodextrin and a colorant such as crystal violet, using the methods described above wherein 4(4-hydroxyphenyl) butan-2-one-2959 (chloro substituted) would be substituted for the dehydrated phthaloylglycine-2959.
EXAMPLE 9
Stabilizing Activity of the Radiation Transorber
This example demonstrates the ability of the present invention to stabilize colorants against light. Victoria Pure Blue BO is admixed in acetonitrile with phthaloylglycine-2959, represented by the following formula: ##STR27## and dehydrated phthaloylglycine-2959, represented by the following formula: ##STR28##
Solutions were prepared according to Table 2. The dye solutions were carefully, uniformly spread on steel plates to a thickness of approximately 0.1 mm. The plates were then immediately exposed to a medium pressure 1200 watt high intensity quartz arc mercury discharge lamp (Conrad-Hanovia, Inc., Newark, N.J.) at a distance of 30 cm from the light. The mercury discharge light is a source of high intensity, broad spectrum light that is used in accelerated fading analysis. Table 2 shows the results of the fade time with the various solutions. Fade time is defined as the time until the dye became colorless to the naked eye.
TABLE 2______________________________________ Victoria pure FadePhthaloylglycine-2959 Blue BO Time______________________________________ 3 parts by weight 1 part by weight 2 min10 parts by weight 1 part by weight 1 1/2 min20 parts by weight 1 part by weight 30 sec______________________________________Dehydrated Victoria pure FadePhthaloylglycine-2959 Blue BO Time______________________________________ 3 parts by weight 1 part by weight 4 min10 parts by weight 1 part by weight 8 min20 parts by weight 1 part by weight >10 min______________________________________
As can be seen in Table 2, when phthaloylglycine-2959 was admixed with Victoria Pure Blue BO, the dye faded when exposed to the mercury discharge light. However, when dehydrated phthaloylglycine-2959 was admixed with the Victoria Pure Blue BO at a ratio of 10 parts dehydrated phthaloylglycine-2959 to one part Victoria Pure Blue BO, there was increased stabilization of the dye to light. When the ratio was 20 parts dehydrated phthaloylglycine-2959 to one part Victoria Pure Blue BO, the dye was substantially stabilized to the mercury discharge light in the time limits of the exposure.
EXAMPLE 10
To determine whether the hydroxy and the dehydroxy 2959 have the capability to stabilize colorants the following experiment was conducted. The following two compounds were tested as described below. ##STR29## 20 parts by weight of the hydroxy and the dehydroxy 2959 were admixed separately to one part by weight of Victoria Pure Blue BO in acetonitrile. The dye solutions were carefully uniformly spread on steel plates to a thickness of approximately 0.1 mm. The plates were then immediately exposed to a mercury discharge light at a distance of 30 cm from the light. The mercury discharge light is a source of high intensity, broad spectrum light that is used in accelerated fading analysis. Table 3 shows the results of the fade time with the various solutions. Fade time is defined as the time until the dye became colorless to the naked eye.
TABLE 3______________________________________ Victoria PureCompound Blue Fade Time______________________________________20 parts 2959 (Hydroxy) 1 part <2 min20 parts 2959 (Dehydroxy) 1 part <2 minNone 1 part <2 min______________________________________
EXAMPLE 11
Stabilizing Activity of the Radiation Transorber and a Molecular Includant
This example demonstrates the capability of dehydrated phthaloylglycine-2959 bound to .beta.-cyclodextrin to stabilize dyes against light. The Victoria Pure Blue BO associated with the radiation transorber, as discussed in the examples above, was tested to determine its capability to stabilize the associated dye against light emitted from a mercury discharge light. In addition, the Victoria Pure Blue BO alone and Victoria Pure Blue BO admixed with .beta.-cyclodextrin were tested as controls. The compositions tested were as follows:
1. Victoria Pure Blue BO only at a concentration of 10 mg/ml in acetonitrile.
2. Victoria Pure Blue BO included in .beta.-cyclodextrin at a concentration of 20 mg/ml in acetonitrile.
3. The Victoria Pure Blue BO included in .beta.-cyclodextrin to which the radiation transorber (dehydrated phthaloylglycine-2959) is covalently attached at a concentration of 20 mg/ml in acetonitrile.
The protocol for testing the stabilizing qualities of the three compositions is as follows: the dye solutions were carefully, uniformly spread on steel plates to a thickness of approximately 0.1 mm. The plates were then immediately exposed to a medium pressure 1200 watt high intensity quartz arc mercury discharge lamp (Conrad-Hanovia, Inc., Newark, N.J.) at a distance of 30 cm from the lamp.
TABLE 4______________________________________ Composition Fade Time______________________________________ 1 5 sec 2 5 sec 3 >10 minutes.sup.a______________________________________ .sup.a There is a phase change after 10 minutes due to extreme heat
As shown in Table 4, only composition number 3, the Victoria Pure Blue BO included in cyclodextrin with the radiation transorber covalently attached to the .beta.-cyclodextrin was capable of stabilizing the dye under the mercury discharge light.
EXAMPLE 12
Preparation of Epoxide Intermediate of Dehydrated Phthaloylglycine-2959
The epoxide intermediate of dehydrated phthaloylglycine 2959 was prepared according to the following reaction: ##STR30##
In a 250 ml, three-necked, round bottomed flask fitted with an addition funnel, thermometer and magnetic stirrer was placed 30.0 g (0.076 mol) of the dehydrated phthaloylglycine-2959, 70 ml methanol and 20.1 ml hydrogen peroxide (30% solution). The reaction mixture was stirred and cooled in a water/ice bath to maintain a temperature in the range 15.degree.-20.degree. C. 5.8 ml of a 6 N NaOH solution was placed in the addition funnel and the solution was slowly added to maintain the reaction mixture temperature of 15.degree.-20.degree. C. This step took about 4 minutes. The mixture was then stirred for 3 hours at about 20.degree.-25.degree. C. The reaction mixture was then poured into 90 ml of water and extracted with two 70 ml portions of ethyl ether. The organic layers were combined and washed with 100 ml of water, dried with anhydrous MgSO.sub.4, filtered, and the ether removed on a rotary evaporator to yield a white solid (yield 20.3 g, 65%). The IR showed the stretching of the C--O--C group and the material was used without further purification.
EXAMPLE 13
Attachment of Epoxide Intermediate to Thiol Cyclodextrin
The attachment of the epoxide intermediate of dehydrated phthaloylglycine 2959 was done according to the following reaction: ##STR31##
In a 250 ml 3-necked round bottomed flask fitted with a stopper and two glass stoppers, all being wired with copper wire and attached to the flask with rubber bands, was placed 30.0 g (0.016 mol) thiol cyclodextrin and 100 ml of anhydrous dimethylformamide (DMF) (Aldrich Chemical Co., Milwaukee, Wis.). The reaction mixture was cooled in a ice bath and 0.5 ml diisopropyl ethyl amine was added. Hydrogen sulfide was bubbled into the flask and a positive pressure maintained for 3 hours. During the last hour, the reaction mixture was allowed to warm to room temperature.
The reaction mixture was flushed with argon for 15 minutes and then poured into 70 ml of water to which was then added 100 ml acetone. A white precipitate occurred and was filtered to yield 20.2 g (84.1%) of a white powder which was used without further purification.
In a 250 ml round bottomed flask fitted with a magnetic stirrer and placed in an ice bath was placed 12.7 g (0.031 mol) epoxide intermediate of dehydrated phthaloylglycine 2959, 80 ml of anhydrous DMF (Aldrich Chemical Co., Milwaukee, Wis.) and 15.0 g (0.010 mol) thiol CD. After the reaction mixture was cooled, 0.5 ml of diisopropyl ethyl amine was added and the reaction mixture stirred for 1 hour at 0.degree. C. to 5.degree. C. followed by 2 hours at room temperature. The reaction mixture was then poured into 200 ml of ice water and a white precipitate formed immediately. This was filtered and washed with acetone. The damp white powder was dried in a convection oven at 80.degree. C. for 3 hours to yield a white powder. The yield was 24.5 g (88%).
EXAMPLE 14
Insertion of Victoria Pure Blue in the Cyclodextrin Cavity
In a 250 ml Erlenmeyer flask was placed a magnetic stirrer, 40.0 g (0.014 mol) of the compound produced in Example 13 and 100 ml water. The flask was heated on a hot plate to 80.degree. C. When the white cloudy mixture became clear, 7.43 g (0.016 mol) of Victoria Pure Blue BO powder was then added to the hot solution and stirred for 10 minutes then allowed to cool to 50.degree. C. The contents were then filtered and washed with 20 ml of cold water.
The precipitate was then dried in a convention oven at 80.degree. C. for 2 hours to yield a blue powder 27.9 g (58.1%).
EXAMPLE 15
The preparation of a tosylated cyclodextrin with the dehydroxy phthaloylglycine 2959 attached thereto is performed by the following reactions: ##STR32##
To a 500 ml 3-necked round bottomed flask fitted with a bubble tube, condenser and addition funnel, was placed 10 g (0.025 mole) of the dehydrated phthaloylglycine 2959 in 150 ml of anhydrous N,N-diethylformamide (Aldrich Chemical Co., Milwaukee, Wis.) cooled to 0.degree. C. in an ice bath and stirred with a magnetic stirrer. The synthesis was repeated except that the flask was allowed to warm up to 60.degree. C. using a warm water bath and the H.sub.2 S pumped into the reaction flask till the stoppers started to move (trying to release the pressure). The flask was then stirred under these conditions for 4 hours. The saturated solution was kept at a positive pressure of H.sub.2 S. The stoppers were held down by wiring and rubber bands. The reaction mixture was then allowed to warm-up overnight. The solution was then flushed with argon for 30 minutes and the reaction mixture poured onto 50 g of crushed ice and extracted three times (3.times.80 ml) with diethyl ether (Aldrich Chemical Co., Milwaukee, Wis.).
The organic layers were condensed and washed with water and dried with MgSO.sub.4. Removal of the solvent on a rotary evaporator gave 5.2 g of a crude product. The product was purified on a silica column using 20% ethyl acetate in hexane as eluant. 4.5 g of a white solid was obtained.
A tosylated cyclodextrin was prepared according to the following reaction: ##STR33##
To a 100 ml round bottomed flask was placed 6.0 g .beta.-cyclodextrin (American Maize Product Company), 10.0 g (0.05 mole) p-toluenesulfonyl chloride (Aldrich Chemical Co., Milwaukee, Wis.), 50 ml of pH 10 buffer solution (Fisher). The resultant mixture was stirred at room temperature for 8 hours after which it was poured on ice (approximately 100 g) and extracted with diethyl ether. The aqueous layer was then poured into 50 ml of acetone (Fisher) and the resultant, cloudy mixture filtered. The resultant white powder was then run through a sephadex column (Aldrich Chemical Co., Milwaukee, Wis.) using n-butanol, ethanol, and water (5:4:3 by volume) as eluant to yield a white powder. The yield was 10.9%.
The degree of substitution of the white powder (tosyl-cyclodextrin) was determined by .sup.13 C NMR spectroscopy (DMF-d6) by comparing the ratio of hydroxysubstituted carbons versus tosylated carbons, both at the 6 position. When the 6-position carbon bears a hydroxy group, the NMR peaks for each of the six carbon atoms are given in Table 5.
TABLE 5______________________________________Carbon Atom NMR Peak (ppm)______________________________________1 101.82 72.93 72.34 81.45 71.96 59.8______________________________________
The presence of the tosyl group shifts the NMR peaks of the 5-position and 6-position carbon atoms to 68.8 and 69.5 ppm, respectively.
The degree of substitution was calculated by integrating the NMR peak for the 6-position tosylated carbon, integrating the NMR peak for the 6-position hydroxy-substituted carbon, and dividing the former by the latter. The integrations yielded 23.6 and 4.1, respectively, and a degree of substitution of 5.9. Thus, the average degree of substitution in this example is about 6.
The tosylated cyclodextrin with the dehydroxy phthaloylglycine 2959 attached was prepared according to the following reaction: ##STR34##
To a 250 ml round bottomed flask was added 10.0 g (4-8 mole) of tosylated substituted cyclodextrin, 20.7 g (48 mmol) of thiol (mercapto dehydrated phthaloylglycine 2959) in 100 ml of DMF. The reaction mixture was cooled to 0.degree. C. in an ice bath and stirred using a magnetic stirrer. To the solution was slowly dropped in 10 ml of ethyl diisopropylamine (Aldrich Chemical Co., Milwaukee, Wis.) in 20 ml of DMF. The reaction was kept at 0.degree. C. for 8 hours with stirring. The reaction mixture was extracted with diethyl ether. The aqueous layer was then treated with 500 ml of acetone and the precipitate filtered and washed with acetone. The product was then run on a sephadex column using n-butanol, ethanol, and water (5:4:3 by volume) to yield a white powder. The yield was 16.7 g.
The degree of substitution of the functionalized molecular includant was determined as described above. In this case, the presence of the derivatized ultraviolet radiation transorber shifts the NMR peak of the 6-position carbon atom to 63.1. The degree of substitution was calculated by integrating the NMR peak for the 6-position substituted carbon, integrating the NMR peak for the 6-position hydroxy-substituted carbon, and dividing the former by the latter. The integrations yielded 67.4 and 11.7, respectively, and a degree of substitution of 5.7. Thus, the average degree of substitution in this example is about 6. The reaction above shows the degree of substitution to be "n". Although n represents the value of substitution on a single cyclodextrin, and therefore, can be from 0 to 24, it is to be understood that the average degree of substitution is about 6.
EXAMPLE 16
The procedure of Example 15 was repeated, except that the amounts of .beta.-cyclodextrin and p-toluenesulfonic acid (Aldrich) were 6.0 g and 5.0 g, respectively. In this case, the degree of substitution of the cyclodextrin was found to be about 3.
EXAMPLE 17
The procedure of Example 15 was repeated, except that the derivatized molecular includant of Example 16 was employed in place of that from Example 15. The average degree of substitution of the functionalized molecular includant was found to be about 3.
EXAMPLE 18
This example describes the preparation of a colored composition which includes a mutable colorant and the functionalized molecular includant from Example 15.
In a 250-ml Erlenmeyer flask containing a magnetic stirring bar was placed 20.0 g (5.4 mmoles) of the functionalized molecular includant obtained in Example 15 and 100 g of water. The water was heated to 80.degree. C., at which temperature a clear solution was obtained. To the solution was added slowly, with stirring, 3.1 g (6.0 mmoles) of Victoria Pure Blue BO (Aldrich). A precipitate formed which was removed from the hot solution by filtration. The precipitate was washed with 50 ml of water and dried to give 19.1 g (84 percent) of a blue powder, a colored composition consisting of a mutable colorant, Victoria Pure Blue BO, and a molecular includant having covalently coupled to it an average of about six ultraviolet radiation transorber molecules per molecular includant molecule.
EXAMPLE 19
The procedure of Example 18 was repeated, except that the functionalized molecular includant from Example 17 was employed in place of that from Example 15.
EXAMPLE 20
This example describes mutation or decolorization rates for the compositions of Examples 7 (wherein the .beta.-cyclodextrin has dehydrated phthaloyl glycine-2959 from Example 4 covalently bonded thereto), 18 and 19.
In each case, approximately 10 mg of the composition was placed on a steel plate (Q-Panel Company, Cleveland, Ohio). Three drops (about 0.3 ml) of acetonitrile (Burdick & Jackson, Muskegon, Mich.) was placed on top of the composition and the two materials were quickly mixed with a spatula and spread out on the plate as a thin film. Within 5-10 seconds of the addition of the acetonitrile, each plate was exposed to the radiation from a 222-nanometer excimer lamp assembly. The assembly consisted of a bank of four cylindrical lamps having a length of about 30 cm. The lamps were cooled by circulating water through a centrally located or inner tube of the lamp and, as a consequence, they operated at a relatively low temperature, i.e., about 50.degree. C. The power density at the lamp's outer surface typically was in the range of from about 4 to about 20 joules per square meter (J/m.sup.2). However, such range in reality merely reflects the capabilities of current excimer lamp power supplies; in the future, higher power densities may be practical. The distance from the lamp to the sample being irradiated was 4.5 cm. The time for each film to become colorless to the eye was measured. The results are summarized in Table 6.
TABLE 6______________________________________Decolorization Times for Various CompositionsComposition Decolorization Times (Seconds)______________________________________Example 18 1Example 19 3-4Example 7 7-8______________________________________
While the data in Table 6 demonstrate the clear superiority of the colored compositions of the present invention, such data were plotted as degree of substitution versus decolorization time. The plot is shown in FIG. 3. FIG. 3 not only demonstrates the significant improvement of the colored compositions of the present invention when compared with compositions having a degree of substitution less than three, but also indicates that a degree of substitution of about 6 is about optimum. That is, the figure indicates that little if any improvement in decolonization time would be achieved with degrees of substitution greater than about 6.
EXAMPLE 21
This example describes the preparation of a complex consisting of a mutable colorant and the derivatized molecular includant of Example 15.
The procedure of Example 18 was repeated, except that the functionalized molecular includant of Example 15 was replaced with 10 g (4.8 mmoles) of the derivatized molecular includant of Example 15 and the amount of Victoria Pure Blue BO was reduced to 2.5 g (4.8 mmoles). The yield of washed solid was 10.8 g (86 percent) of a mutable colorant associated with the .beta.-cyclodextrin having an average of six tosyl groups per molecule of molecular includant.
EXAMPLE 22
This example describes the preparation of a colored composition which includes a mutable colorant and a functionalized molecular includant.
The procedure of preparing a functionalized molecular includant of Example 15 was repeated, except that the tosylated .beta.-cyclodextrin was replaced with 10 g (3.8 mmoles) of the complex obtained in Example 21 and the amount of the derivatized ultraviolet radiation transorber prepared in Example 15 was 11.6 g (27 mmoles). The amount of colored composition obtained was 11.2 g (56 percent). The average degree of substitution was determined as described above, and was found to be 5.9, or about 6.
EXAMPLE 23
The following two compounds were tested for their ability to stabilize Victoria Pure Blue BO: ##STR35##
This example further demonstrates the ability of the present invention to stabilize colorants against light. The two compounds containing Victoria Pure Blue BO as an includant in the cyclodextrin cavity were tested for light fastness under a medium pressure mercury discharge lamp. 100 mg of each compound was dissolved in 20 ml of acetonitrile and was uniformly spread on steel plates to a thickness of approximately 0.1 mm. The plates were then immediately exposed to a medium pressure 1200 watt high intensity quartz arc mercury discharge lamp (Conrad-Hanovia, Inc., Newark, N.J.) at a distance of 30 cm from the lamp. The light fastness results of these compounds are summarized in Table 7.
TABLE 7______________________________________Cyclodextrin Compound Fade Time______________________________________Dehydroxy Compound >10 min.sup.aHydroxy Compound <20 sec______________________________________ .sup.a There is a phase change after 10 minutes due to extreme heat
EXAMPLE 24
This example describes the preparation of films consisting of colorant, ultraviolet radiation transorber, and thermoplastic polymer. The colorant and ultraviolet radiation transorber were ground separately in a mortar. The desired amounts of the around components were weighed and placed in an aluminum pan, along with a weighed amount of a thermoplastic polymer. The pan was placed on a hot plate set at 150.degree. C. and the mixture in the pan was stirred until molten. A few drops of the molten mixture were poured onto a steel plate and spread into a thin film by means of a glass microscope slide. Each steel plate was 3.times.5 inches (7.6 cm.times.12.7 cm) and was obtained from Q-Panel Company, Cleveland, Ohio. The film on the steel plate was estimated to have a thickness of the order of 10-20 micrometers.
In every instance, the colorant was Malachite Green oxalate (Aldrich Chemical Company, Inc., Milwaukee, Wis.), referred to hereinafter as Colorant A for convenience. The ultraviolet radiation transorber ("UVRT") consisted of one or more of IRGACURE.RTM. 500 ("UVRT A"), IRGACURE.RTM. 651 ("UVRT B"), and IRGACURE.RTM. 907 ("UVRT C"), each of which was described earlier and is available from Ciba-Geigy Corporation, Hawthorne, N.Y. The polymer was one of the following: an epichlorohydrin-bisphenol A epoxy resin ("Polymer A"), EPON.RTM. 1004F (Shell Oil Company, Houston, Tex.); a poly(ethylene glycol) having a weight-average molecular weight of about 8,000 ("Polymer B"), CARBOWAX.RTM. 8000 (Aldrich Chemical Company); and a poly(ethylene glycol) having a weight-average molecular weight of about 4,600 ("Polymer C"), CARBOWAX.RTM. 4600 (Aldrich Chemical Company). A control film was prepared which consisted only of colorant and polymer. The compositions of the films are summarized in Table 8.
TABLE 8______________________________________Compositions of Films ContainingColorant and Ultraviolet Radiation Transorber ("UVRT")Colorant UVRT PolymerFilm Type Parts Type Parts Type Parts______________________________________A A 1 A 6 A 90 C 4B A 1 A 12 A 90 C 8C A 1 A 18 A 90 C 12D A 1 A 6 A 90 B 4E A 1 B 30 A 70F A 1 -- -- A 100G A 1 A 6 B 90 C 4H A 1 B 10 C 90______________________________________
While still on the steel plate, each film was exposed to ultraviolet radiation. In each case, the steel plate having the film sample on its surface was placed on a moving conveyor belt having a variable speed control. Three different ultraviolet radiation sources, or lamps, were used. Lamp A was a 222-nanometer excimer lamp and Lamp B was a 308-nanometer excimer lamp, as already described. Lamp C was a fusion lamp system having a "D" bulb (Fusion Systems Corporation, Rockville, Md.). The excimer lamps were organized in banks of four cylindrical lamps having a length of about 30 cm, with the lamps being oriented normal to the direction of motion of the belt. The lamps were cooled by circulating water through a centrally located or inner tube of the lamp and, as a consequence, they operated at a relatively low temperature, i.e., about 50.degree. C. The power density at the lamp's outer surface typically is in the range of from about 4 to about 20 joules per square meter (J/m.sup.2).
However, such range in reality merely reflects the capabilities of current excimer lamp power supplies; in the future, higher power densities may be practical. With Lamps A and B, the distance from the lamp to the film sample was 4.5 cm and the belt was set to move at 20 ft/min (0.1 m/sec). With Lamp C, the belt speed was 14 ft/min (0.07 m/sec) and the lamp-to-sample distance was 10 cm. The results of exposing the film samples to ultraviolet radiation are summarized in Table 9. Except for Film F, the table records the number of passes under a lamp which were required in order to render the film colorless. For Film F, the table records the number of passes tried, with the film in each case remaining colored (no change).
TABLE 9______________________________________Results of Exposing Films ContainingColorant and Ultraviolet Radiation Transorber (UVRT)to Ultraviolet RadiationExcimer LampFilm Lamp A Lamp B Fusion Lamp______________________________________A 3 3 15B 2 3 10C 1 3 10D 1 1 10E 1 1 1F 5 5 10G 3 -- 10H 3 -- 10______________________________________
EXAMPLE 25
This Example demonstrates that the 222 nanometer excimer lamps illustrated in FIG. 4 produce uniform intensity readings on a surface of a substrate 5.5 centimeters from the lamps, at the numbered locations, in an amount sufficient to mutate the colorant in the compositions of the present invention which are present on the surface of the substrate. The lamp 10 comprises a lamp housing 15 with four excimer lamp bulbs 20 positioned in parallel, the excimer lamp bulbs 20 are approximately 30 cm in length. The lamps are cooled by circulating water through a centrally located or inner tube (not shown) and, as a consequence, the lamps are operated at a relatively low temperature, i.e., about 50.degree. C. The power density at the lamp's outer surface typically is in the range of from about 4 to about 20 joules per square meter (J/m.sup.2).
Table 10 summarizes the intensity readings which were obtained by a meter located on the surface of the substrate. The readings numbered 1, 4, 7, and 10 were located approximately 7.0 centimeters from the left end of the column as shown in FIG. 4. The readings numbered 3, 6, 9, and 12 were located approximately 5.5 centimeters from the right end of the column as shown in FIG. 4. The readings numbered 2, 5, 8, and 11 were centrally located approximately 17.5 centimeters from each end of the column as shown in FIG. 4.
TABLE 10______________________________________Background (.mu.W) Reading (mW/cm.sup.2)______________________________________24.57 9.6319.56 9.3522.67 9.3919.62 9.3317.90 9.3019.60 9.3021.41 9.3217.91 9.3023.49 9.3019.15 9.3617.12 9.3521.44 9.37______________________________________
EXAMPLE 26
This Example demonstrates that the 222 nanometer excimer lamps illustrated in FIG. 5 produce uniform intensity readings on a surface of a substrate 5.5 centimeters from the lamps, at the numbered locations, in an amount sufficient to mutate the colorant in the compositions of the present invention which are present on the surface of the substrate. The excimer lamp 10 comprises a lamp housing 15 with four excimer lamp bulbs 20 positioned in parallel, the excimer lamp bulbs 20 are approximately 30 cm in length. The lamps are cooled by circulating water through a centrally located or inner tube (not shown) and, as a consequence, the lamps are operated at a relatively low temperature, i.e., about 50.degree. C. The power density at the lamp's outer surface typically is in the range of from about 4 to about 20 joules per square meter (J/m.sup.2).
Table 11 summarizes the intensity readings which were obtained by a meter located on the surface of the substrate. The readings numbered 1, 4, and 7 were located approximately 7.0 centimeters from the left end of the columns as shown in FIG. 5. The readings numbered 3, 6, and 9 were located approximately 5.5 centimeters from the right end of the columns as shown in FIG. 5. The readings numbered 2, 5, 8 were centrally located approximately 17.5 centimeters from each end of the columns as shown in FIG. 5.
TABLE 11______________________________________Background (.mu.W) Reading (mW/cm.sup.2)______________________________________23.46 9.3216.12 9.3117.39 9.3220.19 9.3116.45 9.2920.42 9.3118.33 9.3215.50 9.3020.90 9.34______________________________________
EXAMPLE 27
This Example demonstrates the intensity produced by the 222 nanometer excimer lamps illustrated in FIG. 6, on a surface of a substrate, as a function of the distance of the surface from the lamps, the intensity being sufficient to mutate the colorant in the compositions of the present invention which are present on the surface of the substrate. The excimer lamp 10 comprises a lamp housing 15 with four excimer lamp bulbs 20 positioned in parallel, the excimer lamp bulbs 20 are approximately 30 cm in length. The lamps are cooled by circulating water through a centrally located or inner tube (not shown) and, as a consequence, the lamps are operated at a relatively low temperature, i.e., about 50.degree. C. The power density at the lamp's outer surface typically is in the range of from about 4 to about 20 joules per square meter (J/m.sup.2).
Table 12 summarizes the intensity readings which were obtained by a meter located on the surface of the substrate at position 1 as shown in FIG. 6. Position 1 was centrally located approximately 17 centimeters from each end of the column as shown in FIG. 6.
TABLE 12______________________________________ ReadingDistance (cm) Background (.mu.W) (mW/cm.sup.2)______________________________________5.5 18.85 9.306.0 15.78 9.3210 18.60 9.3215 20.90 9.3820 21.67 9.4825 19.86 9.6930 22.50 11.1435 26.28 9.1040 24.71 7.5850 26.95 5.20______________________________________
EXAMPLE 28
This example describes a method of making the following wavelength-selective sensitizer: ##STR36##
The wavelength-selective sensitizer is synthesized as summarized below: ##STR37##
To a 250 ml round bottom flask fitted with a magnetic stir bar, and a condensor, was added 10.8 g (0.27 mole) sodium hydroxide (Aldrich), 98 g water and 50 g ethanol. The solution was stirred while being cooled to room temperature in an ice bath. To the stirred solution was added 25.8 g (0.21 mole) acetophenone (Aldrich) and then 32.2 g (0.21 mole) 4-carboxybenzaldehyde (Aldrich). The reaction mixture was stirred at room temperature for approximately 8 hours. The reaction mixture temperature was checked in order to prevent it from exceeding 30.degree. C. Next, dilute HCL was added to bring the mixture to neutral pH. The white/yellow precipitate was filtered using a Buchner funnel to yield 40.0 g (75%) after drying on a rotary pump for four hours. The product was used below without further purification.
The resulting reaction product had the following physical parameters:
Mass. Spec. m/e (m.sup.+) 252, 207, 179, 157, 105, 77, 51.
EXAMPLE 29
This example describes a method of covalently bonding the compound produced in Example 28 to cyclodextrin as is summarized below: ##STR38##
To a 250 ml round bottom flask fitted with a magnetic stir bar, condenser, and while being flushed with argon, was placed 5.0 g (0.019 mole) of the composition prepared in Example 29, and 50 ml of anhydrous DMF (Aldrich). To this solution was slowly dropped in 2.5 g (0.019 mole) oxalyl chloride (Aldrich) over thirty minutes with vigorous stirring while the reaction flask was cooled in an ice-bath. After one hour, the reaction was allowed to warm to room temperature, and then was stirred for one hour. The reaction mixture was used "as is" in the following step. To the above reaction mixture 5.3 g (0.004 mole) of hydroxyethyl substituted alpha-cyclodextrin (American Maize Company), dehydrated by Dean and Stark over benzene for two hours to remove any water, was added and the reaction mixture stirred at room temperature with 3 drops of triethylamine added. After four hours the reaction mixture was poured into 500 ml of acetone and the white precipitate filtered using a Buchner Funnel. The white powder was dried on a rotary pump (0.1 mm Hg) for four hours to yield 8.2 g product.
The resulting reaction product had the following physical parameters:
NMR(DMSO-d.sub.6) .delta.2.80[M, CD], 3.6-4.0 [M, CD], 7.9 [C, aromatus],8.2 [M, aromatus of C], 8.3 [M, aromatus of C] ppm.
EXAMPLE 30
This example describes a method of making the following wavelength-selective sensitizer, namely 4-[4'-carboxy phenyl]-3-buten-2-one: ##STR39##
The wavelength-selective sensitizer is synthesized as summarized below: ##STR40##
The method of Example 28 was followed except that acetone (Fisher, Optima Grade) was added first, and then the carboxybenzaldehyde was added. More particularly, 32.2 g (0.21 mole) of carboxybenzaldehyde was reacted with 12.2 g (0.21 mole) of acetone in the sodium hydroxide/ethanol/water mixture described in Example 28. Dilute HCl was added to bring the reaction mixture to neutral pH, yielding 37.1 g (91%) of a pale yellow powder which was used without further purification in the following examples.
The resulting reaction product, namely 4-[4'-carboxy phenyl]-3-buten-2-one, had the following physical parameters: Mass. Spec. 190 (m.sup.+), 175, 120.
EXAMPLE 31
This example describes a method of covalently bonding the 4-[4'-carboxy phenyl]-3-buten-2-one produced in Example 30 to cyclodextrin as is summarized below: ##STR41##
The method of Example 29 was followed except that 5.0 g of the 4-[4'-carboxy phenyl]-3-buten-2-one was used. More particularly, 5.0 g (0.026 mole) of the 4-[4'-carboxy phenyl]-3-buten-2-one produced in Example 30 was reacted with 3.3 g (0.026 mole) of oxalyl chloride in anyhydrous DMF at about 0.degree. C. Next, approximately 7.1 g (0.005 mole) hydroxyethyl substituted cyclodextrin was added to the mixture (5:1 ratio) under the conditions described in Example 30 and was further processed as described therein, to produce 10.8 g of white powder. The NMR of the product showed both the aromatic protons of the 4-[4'-carboxy phenyl]-3-buten-2-one produced in Example 30 and the glucose protons of the cyclodextrin.
EXAMPLE 32
This example describes a method of covalently bonding the compound produced in Example 28 to a photoreactor, namely IRGACURE.RTM.2959, as is summarized below: ##STR42##
To a 500 ml round bottom flask fitted with a magnetic stir bar, and condensor, was placed 20 g (0.08 mole) of the composition prepared in Example 28, 17.8 g (0.08 mole) IRGACURE.RTM. 2959 (Ciba-Geigy, N.Y.), 0.5 g p-toluenesulfonic acid (Aldrich), and 300 ml anhydrous benzene (Aldrich). The Dean and Stark adapter was put on the flask and the reaction mixture heated at reflux for 8 hours after which point 1.5 ml of water had been collected (theo. 1.43 ml). The reaction mixture was then cooled and the solvent removed on a rotary evaporator to yield 35.4 g. The crude product was recrystalized from 30% ethyl acetate in hexane to yield 34.2 g (94%) of a white powder. The resulting reaction product had the following physical parameters:
Mass. Spectrum: 458 (m.sup.+), 440, 399, 322, 284.
EXAMPLE 33
To determine whether the 4-[4'-carboxy phenyl]-3-buten-2-one produced in Example 30 has the capability to stabilize colorants, the following experiment was conducted. Test films were made up containing 90% CARBOWAX.RTM. 4600 and 10% of a 1 part Victoria Pure Blue BO (Aldrich) to 19 parts 4-[4'-carboxy phenyl]-3-buten-2-one. The mixture was melted on a hot plate, stirred, then drawn down on metal plates (at approximately 60.degree. C.), using a #3 drawdown bar. A similar sample was made with only 1% Victoria Pure Blue BO in 99% CARBOWAX.RTM..
The plates were exposed to a 1200 Watt Mercury medium pressure lamp for one hour, the lamp being about 2 feet from the plates. After one hour, the Victoria Pure Blue BO plate was essentially colorless, while the plate having the mixture of Victoria Pure Blue BO and 4-[4'-carboxy phenyl]-3-buten-2-one thereon had not changed.
EXAMPLE 34
A further experiment to determine the colorant stabilizing capability of the 4-[4'-carboxy phenyl]-3-buten-2-one produced in Example 30 is as follows. The experiment used in Example 33 was repeated except that no CARBOWAX.RTM. was used. Instead, the materials were dissolved in acetonitrile and a film formed, allowed to dry, and then exposed to the 1200 Watt lamp. Again, after one hour, the dye (Victoria Pure Blue BO) was essentially colorless while the mixture containing the 4-[4'-carboxy phenyl]-3-buten-2-one was unchanged in color.
EXAMPLE 35
A further experiment to determine the colorant stabilizing capability of the compounds produced in Examples 28, 29, 30 (4-[4'-carboxy phenyl]-3-buten-2-one), and 31 (4-[4'-carboxy phenyl]-3-buten-2-one/cyclodextrin) was as follows. The experiment used in Example 34 was repeated for all four compounds, separately. More particularly, five metal plates were prepared using the acetonitrile slurry method of Example 34, with the compositions as follows:
(1) Victoria Pure Blue BO only;
(2) Victoria Pure Blue BO+the compound produced in Example 28;
(3) Victoria Pure Blue BO+the compound produced in Example 30;
(4) Victoria Pure Blue BO+the compound produced in Example 29;
(5) Victoria Pure Blue BO+the compound produced in Example 31.
In compositions (2) through (5), the compositions contained one part Victoria Pure Blue BO per 20 parts of the compounds produced in the above examples. More particularly, 0.1 g of Victoria Pure Blue BO was mixed with approximately 2.0 g of one of the compounds produced in the above examples, in 10 ml of acetonitrile. The mixtures were drawn down using a #8 bar and allowed to air dry in a ventilation hood. All of the plates were simultaneously exposed to the 1200 Watt mercury lamp for one hour. Each plate was half covered with aluminum foil during exposure to the lamp to maintain a reference point with respect to fading of the colorant. After one hour under the lamp, mixture (1) had gone colorless, while mixtures (2) through (5) all remained unchanged.
EXAMPLE 36
Another experiment to determine the colorant stabilizing capability of the compound produced in Example 29 was as follows. Briefly described, the compound of Example 29 was used with color inks removed from the color cartridges of a CANON.RTM. BJC-600e bubble jet color printer. The ink was re-installed into the cartridges, which were installed into the ink jet printer, and color test pages were generated. The fortieth color test page was used in the present study.
More particularly, the four cartridges were of BJI-201, and the four inks (cyan, magenta, black, and yellow) were prepared as follows:
(1) Cyan
About 3.8 ml of the colored ink in the cartridge was removed, having a viscosity of 12 seconds for 3 ml measured in a 10 ml pipette. About 0.4 g of the compound produced in Example 29 was added to the 3.8 ml and mixed for 15 minutes. The ink solution prepared was hazy, and had a viscosity of 19 seconds for 3 ml.
(2) Magenta
About 4.8 ml of the colored ink in the cartridge was removed, having a viscosity of 12 seconds for 3 ml. About 0.43 g of the compound of Example 29 was added to the 4.8 ml and mixed for fifteen minutes, producing a ink solution having a viscosity of 18 seconds for 3 ml.
(3) Black
About 7.2 ml of the ink in the cartridge was removed, having a viscosity of 8 seconds for 3 ml. About 0.72 g of the compound of Example 29 was added to the 7.2 ml and mixed for fifteen minutes, producing a hazy ink solution having a viscosity of 15 seconds for 3 ml.
(4) Yellow
About 4.0 ml of the colored ink in the cartridge was removed, having a viscosity of 4 seconds for 3 ml. About 0.41 g of the compound of Example 29 was added to the 4.0 ml and mixed for fifteen minutes, producing a hazy ink solution having a viscosity of 7 seconds for 3 ml.
The cartridges were then refilled with the corresponding ink solutions (1) through (4) above. Forty pages were run off, and the fortieth page was exposed to a 1200 Watt medium pressure mercury lamp with a control sheet for nine hours. The control sheet is the fortieth color test page run off using the ink compositions that were in the original ink cartridges.
The results of this experiment were as follows. After three hours under the 1200 Watt lamp, the control was 40 to 50% bleached, while the inks containing the compound produced in Example 29 were unchanged. After nine hours, the control was 50 to 60% bleached while the inks containing the compound of Example 29 were only about 10 to 20% bleached. Accordingly, the compound produced in Example 29 is capable of stabilizing the dyes found in standard ink jet inks.
EXAMPLE 37
Another experiment to determine the colorant stabilizing capability of the compound produced in Example 29 is as follows. The stability of the ink solutions produced in Example 36 were studied as described below.
The forty-eighth sheet (test sheet) was generated using the ink solutions (1) through (4) of Example 36 each containing about 10% of the compound of Example 29, and was then exposed to a 1200 Watt lamp along with a control sheet (generated from the commercially available ink from the cartridges before the compound of Example 29 was added). The sheets were monitored each hour of exposure and "fade" was determined by the eye against an unexposed sheet. The results of exposing the sheets to the 1200 Watt lamp are summarized in Table 13, where NC.dbd. no change.
TABLE 13______________________________________ IrradiationTime (Hour) Control Sheet Test Sheet______________________________________0 NC NC1 5-10% NC2 10-15% NC3 20% NC4 30% NC5 50% NC______________________________________
Accordingly, the compound prepared in Example 29 works well as a dye stabilizer to visible and ultraviolet radiation.
EXAMPLE 38
This example describes a method of preparing the following wavelength-selective sensitizer: ##STR43##
The wavelength-selective sensitizer is synthesized as summarized below: ##STR44##
To a 250 ml round bottom flask fitted with a magnetic stir bar, is placed 14.6 g (0.097 mole) 4-carboxybenzaldehyde (Aldrich), 13.2 g (0.097 mole) 4'-hydroxyacetophenone (Aldrich), 50 ml of ethanol, 100 ml of water containing 10.8 g sodium hydroxide (Fisher). The solution is stirred at room temperature for four hours after which the reaction mixture is neutralized with hydrochloric acid (2N). The resultant precipitate is filtered on a Buchner funnel and washed with water. The light yellow powder is dried under vacuum for 8 hours to yield 22.1 g, (85%) of product.
The reaction product has the following physical parameters: Mass. Spectrum m/e: 268 (m.sup.+), 245, 218, 193, 179, 151, 125, 73. ##STR45##
A 250 ml round bottom flask is fitted with a Dean and Stark adaptor and condenser. 10.0 g (0.037 mole) of the product produced above in reaction A, 9.36 g (0.037 mole) of the wavelength-selective sensitizer produced in Example 28, 100 ml of dry benzene (Aldrich) and 0.3 g of p-toluene sulfonic acid (Aldrich) are placed into the flask and the reaction mixture heated at reflux for eight hours. The solvent is then removed under reduced pressure to yield a pale yellow solid. The solid is pumped under vacuum to yield 17.2 g (95%) of product.
The reaction product has the following physical parameters:
Mass. Spectrum m/e: 501, 484, 234, 193, 179, 125.
EXAMPLE 39
This example describes a method of preparing the following wavelength-selective sensitizer: ##STR46##
The wavelength-selective sensitizer is synthesized as summarized below: ##STR47##
Into a 250 ml round bottom flask fitted with a Dean and Stark adaptor is placed 10.0 g (0.037 mole) of the product produced in Example 38 (reaction A), 7.1 g (0.037 mole) of the wavelength-selective sensitizer produced in Example 30, 100 ml of dry benzene (Aldrich) and 0.3 g of p-toluene sulfonic acid (Aldrich). The reaction mixture is heated at reflux for eight hours. The solvent is then removed under reduced pressure to yield a light yellow solid. The solid is pumped under vacuum to yield 15.2 g (93%) of product.
The reaction product has the following physical parameters:
Mass. Spectrum m/e: 439 (m.sup.+), 424, 266, 174.
EXAMPLE 40
This example describes a method of covalently bonding the compound produced in Example 38 to cyclodextrin as is summarized below: ##STR48##
First, the compound produced in Example 38 is treated with oxalyl chloride to produce the acid chloride of the compound produced in Example 38. (See Example 29) Next, into a 250 ml round bottom flask fitted with a magnetic stir bar is placed 20.0 g (0.015 mole) of hydroxyethyl-substituted alpha-cyclodextrin (American Maize Company, Hammond, Ind.), 22.2 g (0.030 mole) of the acid chloride form of the wavelength-selective sensitizer produced in Example 38, 100 ml of dry dimethylsulfoxide (Aldrich), and 3 drops of triethylamine. The reaction mixture is stirred for eight hours and then poured into 300 ml of acetone. The resultant white precipitate is filtered, and pumped under vacuum to yield 20.6 g of product.
EXAMPLE 41
This example describes a method of covalently bonding the compound produced in Example 39 to cyclodextrin as is summarized below: ##STR49##
First, the compound produced in Example 39 is treated with oxalyl chloride to form the acid chloride derivative of the compound produced in Example 39. (See Example 29) Into a 250 ml round bottom flask fitted with a magnetic stir bar is placed 20.0 g (0.015 mole) of hydroxyethyl-substituted alpha-cyclodextrin (American Maize Company, Hammond, Ind.), 21.0 g (0.03 mole) of the acid chloride form of the wavelength-selective sensitizer produced in Example 39, 100 ml of dry dimethylsulfoxide (Aldrich), and 3 drops of triethylamine. The reaction mixture is stirred for eight hours and then poured into 300 ml of acetone. The resultant white precipitate is filtered, and pumped under vacuum to yield 22.1 g of product.
EXAMPLE 42
The following three compounds were tested for their ability to stabilize various colorants: ##STR50##
More particularly, this example determines the colorant stabilizing capability of the compounds produced in Examples 29, 40 and 41. Briefly described, the compounds produced in Examples 29, 40 and 41 are used with color inks removed from the ink cartridges (5020036-Black and 5020036-Color) removed from an Epson Stylus Color Printer (Model EscP2) and from the ink removed from the ink cartridges (HP51640Y-yellow, HP51640C-cyan, HP51640M-magenta, and HP51640A-black) removed from an Hewlett-Packard Desk Jet Color Printer (Model 1200C). More particularly, the above ink cartridges are drilled and 5 ml of the ink therein is removed by syringe. Next, an amount of the compound from Examples 29, 40 or 41 is added to the inks from the above cartridges. More particularly, the compounds are measured in moles so that the number of molecules of each compound would be the same. The admixture is mixed for ten minutes, and then placed back into the ink cartridge from which it came, and the hole covered by tape. Table 14 below provides the weights and moles for each of the compounds.
TABLE 14______________________________________CompoundProduced in: Weight of compound in 5 ml (5 g) of ink______________________________________Example 29 0.25 g 0.50 g 0.6 g (5%) (10%) (12%)Example 40 0.33 g 0.66 g 0.81 g (6.6%) (13.2%) (16%)Example 41 0.31 g 0.62 g 0.76 g (6.2%) (12.4%) (15%)Moles 1.2 .times. 10.sup.-4 mole 2.4 .times. 10.sup.-4 mole 2.9 .times. 10.sup.-4 mole______________________________________
The cartridges containing the admixture are then placed back into their respective printers, and 150 color test sheets are generated by the printer. Sheets number 50 and number 100 are then fade tested by exposure to a medium pressure 1200 Watt Mercury Lamp. The sheets are affixed to a poster board with scotch tape, and then are placed approximately 18 inches directly under the lamp. The sheets are exposed for approximately eight hours and then visually compared with unexposed sheets to determine the percentage of fading. Table 15 provides the percent fade of the sheets produced by the Hewlett-Packard Desk Jet 1200C Color Printer, and Table 16 provides the percent face of the sheets produced by the Epson Stylus Color Printer (Model EscP2). The percentages following the identification of the compounds produced in Examples 29, 40, or 41 represent the percent of each compound in the ink composition (weight/weight). Also, "N/C" as used in Tables 15 and 16 represents "no change".
TABLE 15______________________________________Hewlett-Packard DeskJet 1200C Color Printer PercentFade Results % Fade ofCompound # of Pages Sheet % Fade ofProduced in: Concentration Generated #50 Sheet #100______________________________________Control 200 80-90 80-90Example 29 1.2 .times. 10.sup.-4 mole 195 N/C N/C (5%)Example 40 1.2 .times. 10.sup.-4 mole 194 10-15 10-15 (6.6%)Example 41 1.2 .times. 10.sup.-4 mole 194 10-15 10-15 (6.2%)Example 29 2.4 .times. 10.sup.-4 mole 196 N/C N/C (10%)Example 40 2.4 .times. 10.sup.-4 mole 194 5-10 5-10 (13.2%)Example 41 2.4 .times. 10.sup.-4 mole 195 5-10 5-10 (12.4%)Example 29 2.9 .times. 10.sup.-4 mole 198 N/C N/C (12%)Example 40 2.9 .times. 10.sup.-4 mole 196 5-10 5-10 (16%)Example 41 2.9 .times. 10.sup.-4 mole 197 5-10 5-10 (15%)______________________________________
TABLE 16______________________________________Epson Stylus Color Printer (Model EscP2) Percent FadeResults % Fade ofCompound # of Pages Sheet % Fade ofProduced in: Concentration Generated #50 Sheet #100______________________________________Control 153 80-90 80-90Example 29 1.2 .times. 10.sup.-4 mole 152 N/C N/C (5%)Example 40 1.2 .times. 10.sup.-4 mole 153 10-15 10-15 (6.6%)Example 41 1.2 .times. 10.sup.-4 mole 154 10-15 10-15 (6.2%)Example 29 2.4 .times. 10.sup.-4 mole 150 N/C N/C (10%)Example 40 2.4 .times. 10.sup.-4 mole 152 5-10 5-10 (13%)Example 41 2.4 .times. 10.sup.-4 mole 151 5-10 5-10 (12%)Example 29 2.9 .times. 10.sup.-4 mole 152 N/C N/C (12%)Example 40 2.9 .times. 10.sup.-4 mole 150 5-10 5-10 (16%)Example 41 2.9 .times. 10.sup.-4 mole 151 5-10 5-10 (15%)______________________________________
Having thus described the invention, numerous changes and modifications hereof will be readily apparent to those having ordinary skill in the art, without departing from the spirit or scope of the invention.

Claims

1. A colorant stabilizing composition comprising a colorant associated with a compound having the general formula: ##STR51## wherein when R.sub.1 is an aryl group, R.sub.2 is a hydrogen; alkyl; aryl; heterocyclic; or a phenyl group, the phenyl group being substituted with an alkyl, halo, amino, or a thiol group;
wherein when R.sub.2 is an aryl group, R.sub.1 is a hydrogen; alkyl; aryl; heterocyclic; or a phenyl group, the phenyl group being substituted with an alkyl, halo, amino, or a thiol group;
wherein at least one of R.sub.1 and R.sub.2 is an aryl group substituted with one or more carbonyl, ethylene, phenyl, ester, aryl, substituted aryl, or vinylic groups, wherein said groups are sequentially arranged forming a chain of unsaturated groups.
and wherein said composition comprises a substantially uniform distribution of said colorant with said compound.
2. The composition of claim 1, wherein the compound is associated with a molecular includant.
3. The composition of claim 1, wherein the compound has the following formula: ##STR52##
4. The composition of claim 1, wherein the compound has the following formula:
5. The composition of claim 1, wherein the compound has the following formula:
6. The composition of claim 1, wherein the compound has the following formula:
7. A method of light-stabilizing a colorant comprising admixing the colorant with a compound having the formula: wherein when R.sub.1 is an aryl group, R.sub.2 is a hydrogen; alkyl; aryl; heterocyclic; or phenyl group, the phenyl group being substituted with an alkyl, halo, amino, or thiol group;
wherein when R.sub.2 is an aryl group, R.sub.1 is a hydrogen; alkyl; aryl; heterocyclic; or phenyl group, the phenyl group being substituted with an alkyl, halo, amino, or thiol group; and,
wherein at least one of R.sub.1 and R.sub.2 is an aryl group substituted with one or more carbonyl, ethylene, phenyl, ester, aryl, substituted aryl, or vinylic groups, wherein the groups are sequentially arranged forming a chain of unsaturated groups.
8. The method of claim 7, wherein the compound is associated with a molecular includant.
9. The method of claim 7, wherein the compound has the following formula: ##STR53##10.
10. The method of claim 7, wherein the compound has the following formula:
11. The method of claim 7, wherein the compound has the following formula:
12. The method of claim 7, wherein the compound has the following formula:
13. A colorant stabilizing composition comprising a mixture of a colorant and an arylketoalkene stabilizer selected from the group consisting of
14. The composition of claim 13, further comprising a molecular includant.
15. The composition of claim 14, wherein the molecular includant is selected from the group consisting of clathrates, zeolites and cyclodextrins.
16. The composition of claim 15, wherein the cyclodextrin is selected from the group consisting of .alpha.-cyclodextrin, .beta.-cyclodextrin, .gamma.-cyclodextrin, hydroxypropyl .beta.-cyclodextrin, hydroethyl .beta.-cyclodextrin, sulfated .beta.-cyclodextrin, hydroxyethyl .alpha.-cyclodextrin, carboxymethyl .alpha.-cyclodextrin, carboxymethyl .beta.-cyclodextrin, carboxymethyl .gamma.-cyclodextrin, octyl succinated .alpha.-cyclodextrin, octyl succinated .beta.-cyclodextrin, octyl succinated .gamma.-cyclodextrin, and sulfated .gamma.-cyclodextrin.
17. The composition of claim 16, wherein the molecular includant is .beta.-cyclodextrin.
18. The composition of claim 14, wherein the colorant is at least partially included within a cavity of the molecular includant.
19. The composition of claim 14, wherein the molecular includant is covalently bonded to the stabilizer.
20. A method of forming the arylketoalkene stabilizer of claim 13 comprising reacting a compound having a tertiary alcohol in a non-aqueous non-polar solvent in the presence of an effective amount of a transition metal salt to dehydrate the tertiary alcohol, wherein the light-stabilizing compound is represented by the following structures:
21. A method of stabilizing a colorant comprising mixing with the colorant an arylketoalkene stabilizer selected from the group consisting of:
22. The method of claim 21, wherein said composition further comprises a molecular includant.
23. The method of claim 22, wherein the molecular includant is selected from the group consisting of clathrates, zeolites and cyclodextrins.
24. The method of claim 23, wherein the cyclodextrin is selected from the group consisting of .alpha.-cyclodextrin, .beta.-cyclodextrin, .gamma.-cyclodextrin, hydroxypropyl .beta.-cyclodextrin, hydroethyl .beta.-cyclodextrin, sulfated .beta.-cyclodextrin, hydroxyethyl .alpha.-cyclodextrin, carboxymethyl .alpha.-cyclodextrin, carboxymethyl .beta.-cyclodextrin, carboxymethyl .gamma.-cyclodextrin, octyl succinated .alpha.-cyclodextrin, octyl succinated .beta.-cyclodextrin, octyl succinated .gamma.-cyclodextrin, and sulfated .gamma.-cyclodextrin.
25. The method of claim 24, wherein the molecular includant is .beta.-cyclodextrin.
26. The method of claim 22, wherein the colorant is at least partially included within a cavity of the molecular includant.
27. The method of claim 22, wherein the molecular includant is covalently bonded to the stabilizer.
28. A method of forming a light-stabilizing compound comprising: dehydrating a first compound having a tertiary alcohol in a non-aqueous non-polar solvent in the presence of an effective amount of a transition metal salt, wherein the first compound is represented by the formula: ##STR54## and the light stabilizing compound is represented by the formula: ##STR55## wherein: R.sub.5 comprises --CH(R.sub.1)(R.sub.2);
R.sub.1 is a hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;
R.sub.2 is a hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;
R.sub.3 is a hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group; and
R.sub.4 is an aryl, heteroaryl, or substituted aryl group.
29. The method of claim 28, wherein R.sub.1 and R.sub.2 are hydrogen.
30. The method of claim 28, wherein the light stabilizing compound comprises: ##STR56##
31. The method of claim 28, wherein the solvent comprises xylene, benzene toluene, cumene, mesitylene, p-cymene, butylbenzene, styrene, and divinylbenzene.
32. The method of claim 31, wherein the solvent comprises xylene.
33. The method of claim 28, wherein the amount of transition metal salt is an equimolar amount relative to the first compound.
34. The method of claim 28, wherein the dehydrating step takes place at a temperature of from about 80.degree. C. and 150.degree. C.

CROSS-REFERENCE TO RELATED PATENT APPLICATION

This patent application claims the benefit of priority to International Patent Application Ser. No. PCT/US96/04689, filed on Apr. 05, 1996, which claims the benefit of priority to provisional U.S. patent application Ser. No. 60/000,570, filed on Jun. 28, 1995, both of which are incorporated herein by reference.

PCT Information

Filing Document	Filing Date	Country	Kind	102e Date	371c Date
PCT/US96/04689	4/5/1996			12/29/1997	12/29/1997

Publishing Document	Publishing Date	Country	Kind
WO97/01605	1/16/1997

US Referenced Citations (664)

Number	Name	Date
RE28225	Heseltine et al.	Nov 1974
RE28789	Chang	Apr 1976
575228	von Gallois	Jan 1897
582853	Feer	May 1897
893636	Maywald	Jul 1908
1013544	Fuerth	Jan 1912
1325971	Akashi	Dec 1919
1364406	Olsen	Jan 1921
1436856	Brenizer et al.	Nov 1922
1744149	Staehlin	Jan 1930
1803906	Krieger et al.	May 1931
1876880	Drapal	Sep 1932
1880572	Wendt et al.	Oct 1932
1880573	Wendt et al.	Oct 1932
1884199	Bicknell et al.	Feb 1932
1916350	Wendt et al.	Jul 1933
1916779	Wendt et al.	Jul 1933
1955898	Wendt et al.	Apr 1934
1962111	Bamberger	Jun 1934
2005378	Kiel	Jun 1935
2005511	Stoll et al.	Jun 1935
2049005	Gaspar	Jul 1936
2054390	Rust et al.	Sep 1936
2058489	Murch et al.	Oct 1936
2062304	Gaspar	Dec 1936
2090511	Crossley et al.	Aug 1937
2097119	Eggert	Oct 1937
2106539	Schitzspahn	Jan 1938
2111692	Saunders et al.	Mar 1938
2125015	Gaspar	Jul 1938
2130572	Wendt	Sep 1938
2132154	Gaspar	Oct 1938
2145960	Wheatley et al.	Feb 1939
2154996	Rawling	Apr 1939
2159280	Mannes et al.	May 1939
2171976	Erickson	Sep 1939
2181800	Grossley et al.	Nov 1939
2185153	Lecher et al.	Dec 1939
2220178	Schneider	Nov 1940
2230590	Eggert et al.	Feb 1941
2237885	Markush et al.	Apr 1941
2243630	Houk et al.	May 1941
2268324	Polgar	Dec 1941
2281895	van Poser et al.	May 1942
2328166	Poigar et al.	Aug 1943
2346090	Staehle	Apr 1944
2349090	Haddock	May 1944
2356618	Rossander et al.	Aug 1944
2361301	Libby, Jr. et al.	Oct 1944
2364359	Kienle et al.	Dec 1944
2381145	von Glahn et al.	Aug 1945
2382904	Federsen	Aug 1945
2386646	Adams et al.	Oct 1945
2402106	von Glahn et al.	Jun 1946
2416145	Biro	Feb 1947
2477165	Bergstrom	Jul 1949
2527347	Bergstrom	Oct 1950
2580461	Pearl	Jan 1952
2601669	Tullsen	Jun 1952
2612494	von Glahn et al.	Sep 1952
2612495	von Glahn et al.	Sep 1952
2628959	von Glahn et al.	Feb 1953
2647080	Joyce	Jul 1953
2680685	Ratchford	Jun 1954
2728784	Tholstrup et al.	Dec 1955
2732301	Robertson et al.	Jan 1956
2744103	Koch	May 1956
2757090	Meugebauer et al.	Jul 1956
2763550	Lovick	Sep 1956
2768171	Clarke et al.	Oct 1956
2773056	Helfaer	Dec 1956
2798000	Monterman	Jul 1957
2809189	Stanley et al.	Oct 1957
2827358	Kaplan et al.	Mar 1958
2834773	Scalera et al.	May 1958
2875045	Lurie	Feb 1959
2892865	Giraldi et al.	Jun 1959
2897187	Koch	Jul 1959
2936241	Sharp et al.	May 1960
2940853	Sagura et al.	Jun 1960
2955067	McBurney et al.	Oct 1960
2992129	Gauthier	Jul 1961
2992198	Funahashi	Jul 1961
3030208	Schellenberg et al.	Apr 1962
3071815	MacKinnon	Jan 1963
3075014	Palopoli et al.	Jan 1963
3076813	Sharp	Feb 1963
3104973	Sprague et al.	Sep 1963
3114634	Brown et al.	Dec 1963
3121632	Sprague et al.	Feb 1964
3123647	Duennenberger et al.	Mar 1964
3133049	Hertel et al.	May 1964
3140949	Sprague et al.	Jul 1964
3154416	Fidelman	Oct 1964
3155509	Roscow	Nov 1964
3175905	Wiesbaden	Mar 1965
3178285	Anderau et al.	Apr 1965
3238163	O'Neill	Mar 1966
3242215	Heitmiller	Mar 1966
3248337	Zirker et al.	Apr 1966
3266973	Crowley	Aug 1966
3282886	Gadecki	Nov 1966
3284205	Sprague et al.	Nov 1966
3300314	Rauner et al.	Jan 1967
3304297	Wegmann et al.	Feb 1967
3305361	Gaynor et al.	Feb 1967
3313797	Kissa	Apr 1967
3320080	Mazzarella et al.	May 1967
3330659	Wainer	Jul 1967
3341492	Champ et al.	Sep 1967
3359109	Harder et al.	Dec 1967
3361827	Biletch	Jan 1968
3363969	Brooks	Jan 1968
3385700	Willems et al.	May 1968
3397984	Williams et al.	Aug 1968
3415875	Luethi et al.	Dec 1968
3418118	Thommes et al.	Dec 1968
3445234	Cescon et al.	May 1969
3453258	Parmerter et al.	Jul 1969
3453259	Parmerter et al.	Jul 1969
3464841	Skofronick	Sep 1969
3467647	Benninga	Sep 1969
3479185	Chambers	Nov 1969
3502476	Kohei et al.	Mar 1970
3503744	Itano et al.	Mar 1970
3514597	Haes et al.	May 1970
3541142	Cragoe, Jr.	Nov 1970
3546161	Wolheim	Dec 1970
3547646	Hori et al.	Dec 1970
3549367	Chang et al.	Dec 1970
3553710	Lloyd et al.	Jan 1971
3563931	Horiguchi	Feb 1971
3565753	Yurkowitz	Feb 1971
3574624	Reynolds et al.	Apr 1971
3579533	Yalman	May 1971
3595655	Robinson et al.	Jul 1971
3595657	Robinson et al.	Jul 1971
3595658	Gerlach et al.	Jul 1971
3595659	Gerlach et al.	Jul 1971
3607639	Krefeld et al.	Sep 1971
3607693	Heine et al.	Sep 1971
3607863	Dosch	Sep 1971
3615562	Harrison et al.	Oct 1971
3617288	Hartman et al.	Nov 1971
3617335	Kumura et al.	Nov 1971
3619238	Kimura et al.	Nov 1971
3619239	Osada et al.	Nov 1971
3637337	Pilling	Jan 1972
3637581	Horioguchi et al.	Jan 1972
3642472	Mayo	Feb 1972
3647467	Grubb	Mar 1972
3652275	Baum et al.	Mar 1972
3660542	Adachi et al.	May 1972
3667954	Itano et al.	Jun 1972
3668188	King et al.	Jun 1972
3669925	King et al.	Jun 1972
3671096	Mackin	Jun 1972
3671251	Houle et al.	Jun 1972
3676690	McMillin et al.	Jul 1972
3678044	Adams	Jul 1972
3689565	Hoffmann et al.	Sep 1972
3694241	Guthrie et al.	Sep 1972
3695879	Laming et al.	Oct 1972
3697280	Strilko	Oct 1972
3705043	Zablak	Dec 1972
3707371	Files	Dec 1972
3729313	Smith	Apr 1973
3737628	Azure	Jun 1973
3765896	Fox	Oct 1973
3775130	Enomoto et al.	Nov 1973
3788849	Taguchi et al.	Jan 1974
3799773	Watarai et al.	Mar 1974
3800439	Sokolski et al.	Apr 1974
3801329	Sandner et al.	Apr 1974
3817752	Laridon et al.	Jun 1974
3840338	Zviak et al.	Oct 1974
3844790	Chang et al.	Oct 1974
3870524	Watanabe et al.	Mar 1975
3873500	Kato et al.	Mar 1975
3876496	Lozano	Apr 1975
3887450	Gilano et al.	Jun 1975
3895949	Akamatsu	Jul 1975
3901779	Mani	Aug 1975
3910993	Avar et al.	Oct 1975
3914165	Gaske	Oct 1975
3914166	Rudolph et al.	Oct 1975
3915824	McGinniss	Oct 1975
3919323	Houlihan et al.	Nov 1975
3926641	Rosen	Dec 1975
3928264	Young, Jr. et al.	Dec 1975
3933682	Bean	Jan 1976
3952129	Matsukawa et al.	Apr 1976
3960685	Sano et al.	Jun 1976
3965157	Harrison	Jun 1976
3978132	Houlihan et al.	Aug 1976
3984248	Sturmer	Oct 1976
3988154	Sturmer	Oct 1976
4004998	Rosen	Jan 1977
4012256	Levinos	Mar 1977
4017652	Gruber	Apr 1977
4022674	Rosen	May 1977
4024324	Sparks	May 1977
4039332	Kokelenberg et al.	Aug 1977
4043819	Baumann	Aug 1977
4048034	Martan	Sep 1977
4054719	Cordes, III	Oct 1977
4056665	Taylor et al.	Nov 1977
4058400	Crivello	Nov 1977
4067892	Thorne et al.	Jan 1978
4071424	Dart et al.	Jan 1978
4073968	Miyamoto et al.	Feb 1978
4077769	Garcia	Mar 1978
4079183	Green	Mar 1978
4085062	Virgilio et al.	Apr 1978
4090877	Streeper	May 1978
4100047	McCarty	Jul 1978
4105572	Gorondy	Aug 1978
4107733	Schickedanz	Aug 1978
4110112	Roman et al.	Aug 1978
4111699	Krueger	Sep 1978
4114028	Baio et al.	Sep 1978
4126412	Masson et al.	Nov 1978
4141807	Via	Feb 1979
4144156	Kuesters et al.	Mar 1979
4148658	Kondoh et al.	Apr 1979
4162162	Dueber	Jul 1979
4171977	Hasegawa et al.	Oct 1979
4179577	Green	Dec 1979
4181807	Green	Jan 1980
4190671	Vanstone et al.	Feb 1980
4197080	Mee	Apr 1980
4199420	Photis	Apr 1980
4229172	Baumann et al.	Oct 1980
4232106	Iwasaki et al.	Nov 1980
4238492	Majoie	Dec 1980
4239843	Hara et al.	Dec 1980
4239850	Kita et al.	Dec 1980
4241155	Hara et al.	Dec 1980
4242430	Hara et al.	Dec 1980
4242431	Hara et al.	Dec 1980
4245018	Hara et al.	Jan 1981
4245995	Hugl et al.	Jan 1981
4246330	Hara et al.	Jan 1981
4248949	Hara et al.	Feb 1981
4250096	Kvita et al.	Feb 1981
4251622	Kimoto et al.	Feb 1981
4251662	Ozawa et al.	Feb 1981
4254195	Hara et al.	Mar 1981
4256493	Yokoyama et al.	Mar 1981
4256817	Hara et al.	Mar 1981
4258123	Nagashima et al.	Mar 1981
4258367	Mansukhani	Mar 1981
4259432	Kondoh et al.	Mar 1981
4262936	Miyamoto	Apr 1981
4268605	Hara et al.	May 1981
4268667	Anderson	May 1981
4269926	Hara et al.	May 1981
4270130	Houle et al.	May 1981
4271252	Hara et al.	Jun 1981
4271253	Hara et al.	Jun 1981
4272244	Schlick	Jun 1981
4276211	Singer et al.	Jun 1981
4277497	Fromantin	Jul 1981
4279653	Makishima et al.	Jul 1981
4279982	Iwasaki et al.	Jul 1981
4279985	Nonogaki et al.	Jul 1981
4284485	Berner	Aug 1981
4288631	Ching	Sep 1981
4289844	Specht et al.	Sep 1981
4290870	Kondoh et al.	Sep 1981
4293458	Gruenberger et al.	Oct 1981
4298679	Shinozaki et al.	Nov 1981
4300123	McMillin et al.	Nov 1981
4301223	Nakamura et al.	Nov 1981
4302606	Barabas et al.	Nov 1981
4306014	Kunikane et al.	Dec 1981
4307182	Dalzell et al.	Dec 1981
4308400	Felder et al.	Dec 1981
4315807	Felder et al.	Feb 1982
4318705	Nowak et al.	Mar 1982
4318791	Felder et al.	Mar 1982
4321118	Felder et al.	Mar 1982
4335054	Blaser et al.	Jun 1982
4335055	Blaser et al.	Jun 1982
4336323	Winslow	Jun 1982
4343891	Aasen et al.	Aug 1982
4345011	Drexhage	Aug 1982
4347111	Gehlhaus et al.	Aug 1982
4349617	Kawashiri et al.	Sep 1982
4350753	Shelnut et al.	Sep 1982
4351893	Anderson	Sep 1982
4356255	Tachikawa et al.	Oct 1982
4357468	Szejtli et al.	Nov 1982
4359524	Masuda et al.	Nov 1982
4362806	Whitmore	Dec 1982
4367072	Vogtle et al.	Jan 1983
4367280	Kondo et al.	Jan 1983
4369283	Altschuler	Jan 1983
4370401	Winslow et al.	Jan 1983
4372582	Geisler	Feb 1983
4373017	Masukawa et al.	Feb 1983
4373020	Winslow	Feb 1983
4374984	Eichler et al.	Feb 1983
4376887	Greenaway et al.	Mar 1983
4383835	Preuss et al.	May 1983
4390616	Sato et al.	Jun 1983
4391867	Derick et al.	Jul 1983
4399209	Sanders et al.	Aug 1983
4400173	Beavan	Aug 1983
4401470	Bridger	Aug 1983
4416961	Drexhage	Nov 1983
4421559	Owatari	Dec 1983
4424325	Tsunoda et al.	Jan 1984
4425162	Sugiyama	Jan 1984
4425424	Altland et al.	Jan 1984
4426153	Libby et al.	Jan 1984
4434035	Eichler et al.	Feb 1984
4440827	Miyamoto et al.	Apr 1984
4447521	Tiers et al.	May 1984
4450227	Holmes et al.	May 1984
4460676	Fabel	Jul 1984
4467112	Matsuura et al.	Aug 1984
4475999	Via	Oct 1984
4477681	Gehlhaus et al.	Oct 1984
4489334	Owatari	Dec 1984
4495041	Goldstein	Jan 1985
4496447	Eichler et al.	Jan 1985
4500335	Shimada et al.	Feb 1985
4508570	Fugii et al.	Apr 1985
4510392	Litt et al.	Apr 1985
4523924	Lacroix	Jun 1985
4524122	Weber et al.	Jun 1985
4534838	Lin et al.	Aug 1985
4548896	Sabongi et al.	Oct 1985
4555474	Kawamura	Nov 1985
4557730	Bennett et al.	Dec 1985
4564560	Tani et al.	Jan 1986
4565769	Dueber et al.	Jan 1986
4567171	Mangum	Jan 1986
4571377	McGinniss et al.	Feb 1986
4595745	Nakano et al.	Jun 1986
4604344	Irving et al.	Aug 1986
4605442	Kawashita et al.	Aug 1986
4613334	Thomas et al.	Sep 1986
4614723	Schmidt et al.	Sep 1986
4617380	Hinson et al.	Oct 1986
4620875	Shimada et al.	Nov 1986
4620876	Fugii et al.	Nov 1986
4622286	Sheets	Nov 1986
4631085	Kawanishi et al.	Dec 1986
4632891	Banks et al.	Dec 1986
4632895	Patel et al.	Dec 1986
4634644	Irving et al.	Jan 1987
4638340	Iiyama et al.	Jan 1987
4647310	Shimada et al.	Mar 1987
4655783	Reinert et al.	Apr 1987
4663275	West et al.	May 1987
4663641	Iiyama et al.	May 1987
4668533	Miller	May 1987
4672041	Jain	Jun 1987
4698291	Koibuchi et al.	Oct 1987
4701402	Patel et al.	Oct 1987
4702996	Griffing et al.	Oct 1987
4704133	Reinert et al.	Nov 1987
4707161	Thomas et al.	Nov 1987
4707425	Sasagawa et al.	Nov 1987
4707430	Ozawa et al.	Nov 1987
4711668	Shimada et al.	Dec 1987
4711802	Tannenbaum	Dec 1987
4713113	Shimada et al.	Dec 1987
4720450	Ellis	Jan 1988
4721531	Wildeman et al.	Jan 1988
4721734	Gehlhaus et al.	Jan 1988
4724021	Martin et al.	Feb 1988
4724201	Okazaki et al.	Feb 1988
4725527	Robillard	Feb 1988
4727824	Ducharme et al.	Mar 1988
4732615	Kawashita et al.	Mar 1988
4737190	Shimada et al.	Apr 1988
4737438	Ito et al.	Apr 1988
4740451	Kohara	Apr 1988
4745042	Sasago et al.	May 1988
4746735	Kruper, Jr. et al.	May 1988
4752341	Rock	Jun 1988
4755450	Sanders et al.	Jul 1988
4761181	Suzuki	Aug 1988
4766050	Jerry	Aug 1988
4766055	Kawabata et al.	Aug 1988
4770667	Evans et al.	Sep 1988
4772291	Shibanai et al.	Sep 1988
4772541	Gottschalk	Sep 1988
4775386	Reinert et al.	Oct 1988
4786586	Lee et al.	Nov 1988
4789382	Neumann et al.	Dec 1988
4790565	Steed	Dec 1988
4800149	Gottschalk	Jan 1989
4803008	Ciolino et al.	Feb 1989
4808189	Oishi et al.	Feb 1989
4812139	Brodmann	Mar 1989
4812517	West	Mar 1989
4813970	Kirjanov et al.	Mar 1989
4822714	Sanders	Apr 1989
4831068	Reinert et al.	May 1989
4834771	Yamauchi et al.	May 1989
4837106	Ishikawa et al.	Jun 1989
4837331	Yamanishi et al.	Jun 1989
4838938	Tomida et al.	Jun 1989
4839269	Okazaki et al.	Jun 1989
4849320	Irving et al.	Jul 1989
4853037	Johnson et al.	Aug 1989
4853398	Carr et al.	Aug 1989
4854971	Gane et al.	Aug 1989
4857438	Loerzer et al.	Aug 1989
4861916	Kohler et al.	Aug 1989
4865942	Gottschalk et al.	Sep 1989
4874391	Reinert	Oct 1989
4874899	Hoelderich et al.	Oct 1989
4885395	Hoelderich	Dec 1989
4886774	Doi	Dec 1989
4892941	Dolphin et al.	Jan 1990
4895880	Gottschalk	Jan 1990
4900581	Stuke et al.	Feb 1990
4902299	Anton	Feb 1990
4902725	Moore	Feb 1990
4902787	Freeman	Feb 1990
4911732	Neumann et al.	Mar 1990
4911899	Hagiwara et al.	Mar 1990
4917956	Rohrbach	Apr 1990
4921317	Suzuki et al.	May 1990
4925770	Ichiura et al.	May 1990
4925777	Inoue et al.	May 1990
4926190	Lavar	May 1990
4933265	Inoue et al.	Jun 1990
4933948	Herkstroeter	Jun 1990
4937161	Kita et al.	Jun 1990
4942113	Trundle	Jul 1990
4944988	Yasuda et al.	Jul 1990
4950304	Reinert et al.	Aug 1990
4952478	Miyagawa et al.	Aug 1990
4952680	Schmeidl	Aug 1990
4954380	Kanome et al.	Sep 1990
4954416	Wright et al.	Sep 1990
4956254	Washizu et al.	Sep 1990
4964871	Reinert et al.	Oct 1990
4965294	Ohngemach et al.	Oct 1990
4966607	Shinoki et al.	Oct 1990
4966833	Inoue	Oct 1990
4968596	Inoue et al.	Nov 1990
4968813	Rule et al.	Nov 1990
4985345	Hayakawa et al.	Jan 1991
4987056	Imahashi et al.	Jan 1991
4988561	Wason	Jan 1991
4997745	Kawamura et al.	Mar 1991
5001330	Koch	Mar 1991
5002853	Aoai et al.	Mar 1991
5002993	West et al.	Mar 1991
5003142	Fuller	Mar 1991
5006758	Gellert et al.	Apr 1991
5013959	Kogelschatz	May 1991
5017195	Satou et al.	May 1991
5023129	Morganti et al.	Jun 1991
5025036	Carson et al.	Jun 1991
5026425	Hindagolla et al.	Jun 1991
5026427	Mitchell et al.	Jun 1991
5028262	Barlow, Jr. et al.	Jul 1991
5028792	Mullis	Jul 1991
5030243	Reinert	Jul 1991
5030248	Meszaros	Jul 1991
5034526	Bonham et al.	Jul 1991
5037726	Kojima et al.	Aug 1991
5045435	Adams et al.	Sep 1991
5045573	Kohler et al.	Sep 1991
5047556	Kohler et al.	Sep 1991
5049777	Mechtersheimer	Sep 1991
5053320	Robbillard	Oct 1991
5055579	Pawlowski et al.	Oct 1991
5057562	Reinert	Oct 1991
5068364	Takagaki et al.	Nov 1991
5069681	Bouwknegt et al.	Dec 1991
5070001	Stahlhofen	Dec 1991
5073448	Vieira et al.	Dec 1991
5074885	Reinert	Dec 1991
5076808	Hahn et al.	Dec 1991
5085698	Ma et al.	Feb 1992
5087550	Blum et al.	Feb 1992
5089050	Vieira et al.	Feb 1992
5089374	Saeva	Feb 1992
5096456	Reinert et al.	Mar 1992
5096489	Laver	Mar 1992
5096781	Vieira et al.	Mar 1992
5098477	Vieira et al.	Mar 1992
5098793	Rohrbach et al.	Mar 1992
5098806	Robillard	Mar 1992
5106723	West et al.	Apr 1992
5108505	Moffat	Apr 1992
5108874	Griffing et al.	Apr 1992
5110706	Yumoto et al.	May 1992
5110709	Aoai et al.	May 1992
5114832	Zertani et al.	May 1992
5124723	Laver	Jun 1992
5130227	Wade et al.	Jul 1992
5133803	Moffatt	Jul 1992
5135940	Belander et al.	Aug 1992
5139572	Kawashima	Aug 1992
5139687	Borgher, Sr. et al.	Aug 1992
5141556	Matrick	Aug 1992
5141797	Wheeler	Aug 1992
5144964	Demian	Sep 1992
5147901	Rutsch et al.	Sep 1992
5153104	Rossman et al.	Oct 1992
5153105	Sher et al.	Oct 1992
5153166	Jain et al.	Oct 1992
5160346	Fuso et al.	Nov 1992
5160372	Matrick	Nov 1992
5166041	Murofushi et al.	Nov 1992
5169436	Matrick	Dec 1992
5169438	Matrick	Dec 1992
5173112	Matrick et al.	Dec 1992
5176984	Hipps, Sr. et al.	Jan 1993
5178420	Shelby	Jan 1993
5180425	Matrick et al.	Jan 1993
5180624	Kojima et al.	Jan 1993
5180652	Yamaguchi et al.	Jan 1993
5181935	Reinert et al.	Jan 1993
5185236	Shiba et al.	Feb 1993
5187045	Bonham et al.	Feb 1993
5187049	Sher et al.	Feb 1993
5190565	Berenbaum et al.	Mar 1993
5190710	Kletecka	Mar 1993
5190845	Hashimoto et al.	Mar 1993
5193854	Borowski, Jr. et al.	Mar 1993
5196295	Davis	Mar 1993
5197991	Rembold	Mar 1993
5198330	Martic et al.	Mar 1993
5202209	Winnik et al.	Apr 1993
5202210	Matsuoka et al.	Apr 1993
5202211	Vercoulen	Apr 1993
5202212	Shin et al.	Apr 1993
5202213	Nakahara et al.	Apr 1993
5202215	Kanakura et al.	Apr 1993
5202221	Imai et al.	Apr 1993
5205861	Matrick	Apr 1993
5208136	Zanoni et al.	May 1993
5209814	Felten et al.	May 1993
5219703	Bugner et al.	Jun 1993
5221334	Ma et al.	Jun 1993
5224197	Zanoni et al.	Jun 1993
5224987	Matrick	Jul 1993
5226957	Wickramanayake et al.	Jul 1993
5227022	Leonhardt et al.	Jul 1993
5241059	Yoshinaga	Aug 1993
5244476	Schulz et al.	Sep 1993
5250109	Chan et al.	Oct 1993
5254429	Gracia et al.	Oct 1993
5256193	Winnik et al.	Oct 1993
5258274	Helland et al.	Nov 1993
5261953	Vieira et al.	Nov 1993
5262276	Kawamura	Nov 1993
5268027	Chan et al.	Dec 1993
5270078	Walker et al.	Dec 1993
5271764	Winnik et al.	Dec 1993
5271765	Ma	Dec 1993
5272201	Ma et al.	Dec 1993
5275646	Marshall et al.	Jan 1994
5279652	Kaufmann et al.	Jan 1994
5282894	Albert et al.	Feb 1994
5284734	Blum et al.	Feb 1994
5286286	Winnik et al.	Feb 1994
5286288	Tobias et al.	Feb 1994
5294528	Furutachi	Mar 1994
5296275	Coman et al.	Mar 1994
5296556	Frihart	Mar 1994
5298030	Burdeska et al.	Mar 1994
5300403	Angelopolus et al.	Apr 1994
5300654	Nakajima et al.	Apr 1994
5302195	Helbrecht	Apr 1994
5302197	Wickramanayke et al.	Apr 1994
5310778	Shor et al.	May 1994
5312713	Yokoyama et al.	May 1994
5312721	Gesign	May 1994
5324349	Sano et al.	Jun 1994
5328504	Ohnishi	Jul 1994
5330860	Grot et al.	Jul 1994
5334455	Noren et al.	Aug 1994
5338319	Kaschig et al.	Aug 1994
5340631	Matsuzawa et al.	Aug 1994
5340854	Martic et al.	Aug 1994
5344483	Hinton	Sep 1994
5356464	Hickman et al.	Oct 1994
5362592	Murofushi et al.	Nov 1994
5368689	Agnemo	Nov 1994
5372387	Wajda	Dec 1994
5372917	Tsuchida et al.	Dec 1994
5374335	Lindgren et al.	Dec 1994
5376503	Audett et al.	Dec 1994
5383961	Bauer et al.	Jan 1995
5384186	Trinh	Jan 1995
5393580	Ma et al.	Feb 1995
5401303	Stoffel et al.	Mar 1995
5401562	Akao	Mar 1995
5415686	Kurabayashi et al.	May 1995
5415976	Ali	May 1995
5424407	Tanaka et al.	Jun 1995
5425978	Berneth et al.	Jun 1995
5426164	Babb et al.	Jun 1995
5427415	Chang	Jun 1995
5429628	Trinh et al.	Jul 1995
5431720	Nagai et al.	Jul 1995
5432274	Luong et al.	Jul 1995
5445651	Thoen et al.	Aug 1995
5445842	Tanaka et al.	Aug 1995
5455074	Nohr et al.	Oct 1995
5455143	Ali	Oct 1995
5459014	Nishijima et al.	Oct 1995
5464472	Horn et al.	Nov 1995
5466283	Kondo et al.	Nov 1995
5474691	Severns	Dec 1995
5475080	Gruber et al.	Dec 1995
5476540	Shields et al.	Dec 1995
5479949	Battard et al.	Jan 1996
5489503	Toan	Feb 1996
5498345	Jollenbeck et al.	Mar 1996
5501774	Burke	Mar 1996
5503664	Sano et al.	Apr 1996
5509957	Toan et al.	Apr 1996
5531821	Wu	Jul 1996
5532112	Kohler et al.	Jul 1996
5541633	Winnik et al.	Jul 1996
5543459	Hartmann et al.	Aug 1996
5569529	Becker et al.	Oct 1996
5571313	Mafune et al.	Nov 1996
5575891	Trokhan et al.	Nov 1996
5580369	Belding et al.	Dec 1996
5591489	Dragner et al.	Jan 1997
5607803	Murofushi et al.	Mar 1997
5616443	Nohr et al.	Apr 1997
5635297	Ogawa et al.	Jun 1997
5643356	Nohr et al.	Jul 1997
5643631	Donigian et al.	Jul 1997
5643701	Nohr et al.	Jul 1997
5645964	Nohr et al.	Jul 1997
5672392	De Clereq et al.	Sep 1997
5681380	Nohr et al.	Oct 1997
5683843	Nohr et al.	Nov 1997
5685754	Nohr et al.	Nov 1997
5686503	Nohr et al.	Nov 1997
5700582	Sargeant et al.	Dec 1997
5700850	Nohr et al.	Dec 1997
5705247	Arai et al.	Jan 1998
5709955	Nohr et al.	Jan 1998
5709976	Malhotra	Jan 1998
5721287	Nohr et al.	Feb 1998
5733693	Nohr et al.	Mar 1998
5739175	Nohr et al.	Apr 1998
5747550	Nohr et al.	May 1998
5773182	Nohr et al.	Jun 1998
5782963	Nohr et al.	Jul 1998
5786132	Nohr et al.	Jul 1998
5798015	Nohr et al.	Aug 1998
5811199	MacDonald et al.	Sep 1998
5837429	Nohr et al.	Nov 1998
5849411	Nohr et al.	Dec 1998
5855655	Nohr et al.	Jan 1999
5865471	Nohr et al.	Feb 1999

Foreign Referenced Citations (213)

Number	Date	Country
103085	Apr 1937	AUX
1262488	Sep 1988	AUX
620075	May 1962	BEX
637169	Mar 1964	BEX
413257	Oct 1932	CAX
458808	Dec 1936	CAX
460268	Oct 1949	CAX
461082	Nov 1949	CAX
463022	Feb 1950	CAX
463021	Feb 1950	CAX
465495	May 1950	CAX
465499	May 1950	CAX
465496	May 1950	CAX
483214	May 1952	CAX
517364	Oct 1955	CAX
537687	Mar 1957	CAX
552565	Feb 1958	CAX
571792	Mar 1959	CAX
779239	Feb 1968	CAX
930103	Jul 1973	CAX
2053094	Apr 1992	CAX
94118	May 1958	CZX
0003884	Sep 1979	EPX
0029284	May 1981	EPX
0127574	Dec 1984	EPX
0223587	May 1987	EPX
0262533	Apr 1988	EPX
0280458	Aug 1988	EPX
0308274	Mar 1989	EPX
0351615	Jan 1990	EPX
0375160	Jun 1990	EPX
0371304	Jun 1990	EPX
0373662	Jun 1990	EPX
0390439	Oct 1990	EPX
0458140A1	Oct 1991	EPX
0458140	Nov 1991	EPX
0468465	Jan 1992	EPX
0542286	May 1993	EPX
000571190	Nov 1993	EPX
0608433	Aug 1994	EPX
0609159	Aug 1994	EPX
0639664	Feb 1995	EPX
0 716 929	Jun 1996	EPX
0755984	Jan 1997	EPX
2245010	Apr 1975	FRX
2383157	Oct 1978	FRX
1047787	Dec 1957	DEX
1022801	Jan 1958	DEX
1039835	Sep 1958	DEX
1040562	Oct 1958	DEX
1047013	Dec 1958	DEX
1045414	Dec 1958	DEX
1132450	Jul 1962	DEX
1132540	Jul 1962	DEX
1154069	Sep 1963	DEX
1240811	May 1967	DEX
2202497	Aug 1972	DEX
2432563	Feb 1975	DEX
2437380	Feb 1975	DEX
2444520	Mar 1975	DEX
2416259	Oct 1975	DEX
2714978	Oct 1977	DEX
2722264	Nov 1978	DEX
3126433	Jan 1983	DEX
158237	Jan 1983	DEX
3415033	Oct 1984	DEX
271512	Sep 1989	DEX
3921600	Jan 1990	DEX
3833438	Apr 1990	DEX
3833437	Apr 1990	DEX
004036328	Jul 1991	DEX
4132288	Apr 1992	DEX
41226461	Feb 1993	DEX
662500	Apr 1964	ITX
43-15663	Jul 1968	JPX
47-26653	Jul 1972	JPX
47-45409	Nov 1972	JPX
49-8909	Feb 1974	JPX
50-65592	Jun 1975	JPX
51-17802	Feb 1976	JPX
53-104321	Sep 1978	JPX
55-62059	May 1980	JPX
55-90506	Jul 1980	JPX
56-8134	Jan 1981	JPX
0014233	Feb 1981	JPX
56-14569	Feb 1981	JPX
56-24472	Mar 1981	JPX
56-36556	Apr 1981	JPX
57-61055	Apr 1982	JPX
57-128283	Aug 1982	JPX
57-171775	Oct 1982	JPX
58-124452	Jul 1983	JPX
58-125770	Jul 1983	JPX
58-222164	Dec 1983	JPX
59-89360	May 1984	JPX
29219270	Dec 1984	JPX
59-219270	Apr 1985	JPX
60-192729	Oct 1985	JPX
60-239741	Nov 1985	JPX
60-239739	Nov 1985	JPX
60-239740	Nov 1985	JPX
60-239743	Nov 1985	JPX
61-288	Jan 1986	JPX
61-3781	Jan 1986	JPX
61-14995	Jan 1986	JPX
61-14994	Jan 1986	JPX
61-21184	Jan 1986	JPX
61-25885	Feb 1986	JPX
61-30592	Feb 1986	JPX
61-40366	Feb 1986	JPX
61-77846	Apr 1986	JPX
61-128973	Jun 1986	JPX
61-97025	Sep 1986	JPX
61-222789	Oct 1986	JPX
61-247703	Nov 1986	JPX
61-285403	Dec 1986	JPX
62-7703	Jan 1987	JPX
62-97881	May 1987	JPX
62-100557	May 1987	JPX
62100557	May 1987	JPX
62-127281	Jun 1987	JPX
63-43959	Feb 1988	JPX
63-48370	Mar 1988	JPX
63-95447	Apr 1988	JPX
63-95446	Apr 1988	JPX
63-95440	Apr 1988	JPX
63-95439	Apr 1988	JPX
63-95450	Apr 1988	JPX
63-95449	Apr 1988	JPX
63-95448	Apr 1988	JPX
63-95445	Apr 1988	JPX
63-151946	Jun 1988	JPX
63-165498	Jul 1988	JPX
63-164953	Jul 1988	JPX
63-223078	Sep 1988	JPX
63-223077	Sep 1988	JPX
63-243101	Oct 1988	JPX
63-199781	Dec 1988	JPX
64-29337	Jan 1989	JPX
64-15049	Jan 1989	JPX
64-40948	Feb 1989	JPX
89014948	Mar 1989	JPX
1-128063	May 1989	JPX
1146974	Jun 1989	JPX
01210477	Aug 1989	JPX
424756	Sep 1989	JPX
1288854	Nov 1989	JPX
2-58573	Feb 1990	JPX
292957	Apr 1990	JPX
2179642	Jul 1990	JPX
2282261	Nov 1990	JPX
3-134072	Jun 1991	JPX
3-170415	Jul 1991	JPX
03163566	Jul 1991	JPX
3-206439	Sep 1991	JPX
5134447	Nov 1991	JPX
3-258867	Nov 1991	JPX
3-203694	Dec 1991	JPX
3284668	Dec 1991	JPX
4023884	Jan 1992	JPX
4023885	Jan 1992	JPX
4-45174	Feb 1992	JPX
4100801	Apr 1992	JPX
4-136075	May 1992	JPX
04356087	Dec 1992	JPX
543806	Feb 1993	JPX
561220	Mar 1993	JPX
5080506	Apr 1993	JPX
05119506	May 1993	JPX
5-140498	Jun 1993	JPX
2-219869	Sep 1993	JPX
5263067	Oct 1993	JPX
680915	Mar 1994	JPX
6116577	Apr 1994	JPX
6116556	Apr 1994	JPX
6116555	Apr 1994	JPX
6-175584	Jun 1994	JPX
6214339	Aug 1994	JPX
6256633	Sep 1994	JPX
6256494	Sep 1994	JPX
7113828	Apr 1972	NLX
1310767	May 1987	RUX
603767	Aug 1978	CHX
197808	May 1988	CHX
1772118	Oct 1992	SUX
275245	Oct 1928	GBX
349339	May 1931	GBX
355686	Aug 1931	GBX
399753	Oct 1933	GBX
441085	Jan 1936	GBX
463515	Apr 1937	GBX
492711	Sep 1938	GBX
518612	Mar 1940	GBX
539912	Sep 1941	GBX
626727	Jul 1947	GBX
600451	Apr 1948	GBX
616362	Jan 1949	GBX
618616	Feb 1949	GBX
779389	Jul 1959	GBX
1372884	Nov 1974	GBX
2146357	Apr 1985	GBX
9211295	Jul 1992	WOX
9306597	Apr 1993	WOX
9401503	Jan 1994	WOX
9422500	Oct 1994	WOX
9422501	Oct 1994	WOX
WO 9504955	Feb 1995	WOX
9528285	Oct 1995	WOX
9600740	Jan 1996	WOX
9619502	Jun 1996	WOX
WO 9622335	Jul 1996	WOX
9624636	Aug 1996	WOX
9720000	Jun 1997	WOX

Non-Patent Literature Citations (224)

Entry
Kubat et al. "Photophysical properties of metal complexes of meso-tetrakis (40sulphonatophenyl) porphyrin," J. Photochem. and Photobiol. 96 93-97 1996, no month available.
Abstract for WO 95/00343--A1 Textiles: Paper: Cellulose p. 7 1995, no month available.
Maki, Y. et al. "A novel heterocyclic N-oxide, pyrimido[5,4-g]pteridinetetrone 5-oxide, with multifunctional photooxidative properties" Chemical Abstracts 122 925 [No. 122:31350 F] 1995, no month available.
Abstract of patent, JP 6-80915 (Canon Inc.), Mar. 22, 1994.
Abstract of patent, JP 06-43573 (Iku Meji) (Feb. 18, 1994).
Pitchumani, K. et al. "Modification of chemical reactivity upon cyclodextrin encapsulation" Chemical Abstracts 121 982 [No. 121:13362 4v] 1994, no month available.
Derwent Publications Ltd., London, JP 05297627 (Fujitsu Ltd.), Nov. 12, 1993. (Abstract).
Patent Abstracts of Japan, JP 5241369 (Bando Chem Ind Ltd et al.), Sep. 21, 1993. (Abstract).
Derwent Publications Ltd., London, JP 05232738 (Yamazaki, T.), Sep. 10, 1993. (Abstract).
Derwent Publications Ltd., London, EP 000559310 (Zeneca Ltd.), Sep. 8, 1993. (Abstract).
Derwent Publications Ltd., London, J,A, 5-230410 (Seiko Epson Corp), Sep. 7, 1993. (Abstract).
Derwent Publications Ltd., London, JP 5-230407 (Mitsubishi Kasei Corp), Sep. 7, 1993. (Abstract).
Abstract Of Patent, JP 405230410 (Seiko Epson Corp.), Sep. 7, 1993. (Abstract).
Abstract Of Patent, JP 405230407 (Mitsubishi Kasei Corp.), Sep. 7, 1993. (Abstract).
Patent Abstracts of Japan, JP 5197198 (Bando Chem Ind Ltd et al.), Aug. 6, 1993. (Abstract).
Database WPI -Derwent Publications Ltd., London, J,A, 5197069 (Bando Chem), Aug. 6, 1993. (Abstract).
Abstract of patent, JP 5-195450 (Nitto Boseki Co. Ltd), Aug. 3, 1993.
Patent Abstracts of Japan, JP5181308 (Bando Chem Ind Ltd et al.), Jul. 23, 1993. (Abstract).
Patent Abstracts of Japan, JP 5181310 (Bando Chem Ind Ltd et al.), Jul. 23, 1993. (Abstract).
Derwent Publications Ltd., London, JP 5-132638 (Mitsubishi Kasei Corp), May 28, 1993. (Abstract).
Abstract Of Patent, JP 405132638 (Mitsubishi Kasei Corp.), May 28, 1993. (Abstract).
Derwent Publications Ltd., London, JP 5-125318 (Mitsubishi Kasei Corp), May 21, 1993. (Abstract).
"Cyclodextrins: A Breakthrough for Molecular Encapsulation" American Maize Products Co. (AMAIZO) 1993, no month available.
Abstract of patent, JP 05-117200 (Hidefumi Hirai et al.) (May 14, 1993).
Derwent World Patents Index, JP 5117105 (Mitsui Toatsu Chem Inc.) May 14, 1993.
Derwent Publications Ltd., London, JP 05061246 (Ricoh KK), Mar. 12, 1993. (Abstract).
Husain, N. et al. "Cyclodextrins as mobile-phase additives in reversed-phase HPLC" American Laboratory 82 80-87 1993, no month available.
Hamilton, D.P. "Tired of Shredding? New Ricoh Method Tries Different Tack" Wall Street Journal B2 1993, no month available.
"Cyclodextrins: A Breakthrough for Molecular Encapsulation" American Maize Products Co. (AMAIZO) 1993, no month available.
Duxbury "The Photochemistry and Photophysics of Triphenylmethane Dyes in Solid Liquid Media" Chemical Review 93 381-433 1993, no month available.
Abstract of patent, JP 04-351603 (Dec. 7, 1992).
Abstract of patent, JP 04-351602 1992, no month available.
Derwent Publications Ltd., London, JP 404314769 (Citizen Watch Co. Ltd.), Nov. 5, 1992. (Abstract).
Abstract of patent, JP 04315739 1992, no month available.
Derwent Publications Ltd., London, JP 04300395 (Funai Denki KK), Oct. 23, 1992. (Abstract).
Derwent Publications Ltd., London, JP 404213374 (Mitsubishi Kasei Corp), Aug. 4, 1992. (Abstract).
Abstract of patent, JP 04-210228 1992, no month available.
Abstract Of Patent, JP 404202571 (Canon Inc.), Jul. 23, 1992. (Abstract).
Abstract Of Patent, JP 404202271 (Mitsubishi Kasei Corp.), Jul. 23, 1992. (Abstract).
Derwent Publications Ltd., London, JP 4-189877 (Seiko Epson Corp), Jul. 8, 1992. (Abstract).
Derwent Publications Ltd., London, JP 404189876 (Seiko Epson Corp), Jul. 8, 1992. (Abstract).
Abstract Of Patent, JP 404189877 (Seiko Epson Corp.), Jul. 8, 1992. (Abstract).
Derwent Publications Ltd., London, J,A, 4-170479 (Seiko Epson Corp), Jun. 18, 1992. (Abstract).
Abstract of patent, JP 04-81402 1992, no month available.
Abstract of patent, JP 04-81401 1992, no month available.
Kogelschatz "Silent-discharge driven excimer UV sources and their applications" Applied Surface Science 410-423 1992, no month available.
Derwent Publications, Ltd., London, JP 403269167 (Japan Wool Textile KK), Nov. 29, 1991 (Abstract).
Derwent Publications Ltd., London, JO 3247676 (Canon KK), Nov. 5, 1991 (Abstract).
Abstract of patent, JP 03-220384 1991, no month available.
Patent Abstracts of Japan, JP 03184896 (Dainippon Printing Co Ltd.) Aug. 12 1991.
Derwent Publications Ltd., London, JP 3167270 (Mitsubishi Kasei Corp), Aug. 19, 1991. (Abstract).
Derwent Publications Ltd., London, JO 3167270 (Mitsubishi Kasei Corp.), Jul. 19, 1991. (Abstract).
Derwent Publications Ltd., London, JO 3093870 (Dainippon Ink Chem KK.), Apr. 18, 1991 (Abstract).
Abstract of patent, JP 06369890 1991, no month available.
Kogelschatz, U. et al. "New Excimer UV Sources for Industrial Applications" ABB Review 391 1-10 1991, no month available.
Abstract of patent, JP 03-41165 1991, no month available.
"Coloring/Decoloring Agent for Tonor Use Developed" Japan Chemical Week 1991, no month available.
Braithwaite, M., et al. "Formulation" Chemistry & Technology of UV & EB Formulation for Coating, Inks & Paints IV 11-12 1991, no month available.
Scientific Polymer Products, Inc. Brochure 24-31, 1991, no month available.
Dietliker, K. "Photoiniators for Free Radical and Cationic Polymerisation" Chem & Tech of UV & EB Formulation for Coating, Inks & Paints III 61, 63, 229-232, 280, 405, 1991, no month available.
Esrom et al. "Large area Photochemical Dry Etching of Polymers iwth Incoherent Excimer UV Radiation" MRS Materials Research Society 1-7 1991, no month available.
Esrom et al. Excimer Laser-Induced Decompostion of Aluminum Nitride Materials Research Society Fall Meeting 1-6 1991, no month available.
Esrom et al. "Metal deposition with a windowless VUV excimer source" Applied Surface Science 1-5 1991, no month available.
Esrom "Excimer Laser-Induced Surface Activation of Aln for Electroless Metal Deposition" Mat. Res. Sco.1Symp. Proc. 204 457-465 1991, no month available.
Zhang et al. "UV-induced decompositin of adsorbed Cu-acetylacetonate films at room temperature for electroless metal plating" Applied Surface Science 1-6 1991, no month available.
"German company develops reuseable paper" Pulp & Paper 1991, no month available.
Abstract of patent, JP 02289652 1990, no month available.
Ohashi et al. "Molecular Mechanics Studies on Inclusion Compounds of Cyanine Dye Monomers and Dimers in Cyclodextrin Cavities," J. Am. Chem. Soc. 112 5824-5830 1990, no month available.
Kogelschatz et al. "New Incoherent Ultraviolet Excimer Sources for Photolytic Material Deposition," Laser Und Optoelektronik 1990, no month available.
Patent Abstracts of Japan, JP 02141287 (Dainippon Printing Co Ltd.) May 30, 1990, no month available.
Abstract of Patent, JP 0297957, (Fuji Xerox Co., Ltd.) 1990, no month available.
Derwent Publications Ltd., London, JP 2091166 (Canon KK), Mar. 30, 1990. (Abstract).
Esrom et al. "Metal Deposition with Incoherent Excimer Radiation" Mat. Res. Symp. Proc. 158 189-198 1990, no month available.
Esrom "UV Excimer Laer-Induced Deposition of Palladium from palladiym Acetate Films" Mat. Res. Soc. Symp. Proc. 158 109-117 1990, no month available.
Kogelschatz, U. "Silent Discharges for the Generation of ultraviolet and vacuum ultraviolet excimer radiation" Pure & Applied Chem. 62 1667-74 1990, no month available.
Esrom et al. "Investigation of the mechanism of the UV-induced palladium depostions processf from thin solid palladium acetate films" Applied Surface Science 46 158-162 1990, no month available.
Zhang et al. "VUV synchrotron radiation processing of thin palladium acetate spin-on films for metallic surface patterning" Applied Surface Science 46 153-157 1990, no month available.
Brennan et al. "Tereolectronic effects in ring closure reactions: the 2'-hydroxychalcone--flavonone equilibrium, and related systems," Canadian J. Chem. 68 (10) pp. 1780-1785 1990, no month available.
Abstract of patent, JP 01-299083 1989, no month available.
Derwent Publications Ltd., London, J,O, 1182379 (Canon KK), Jul. 20, 1989. (Abstract).
Derwent Publications Ltd., London, JO 1011171 (Mitsubishi Chem Ind. KK.), Jan. 13, 1989 (Abstract).
Gruber, R.J., et al. "Xerographic Materials" Encyclopedia of Polymer Science and Engineering 17 918-943 1989, no month available.
Pappas, S.P. "Photocrosslinking" Comph. Pol. Sci. 6 135-148 1989, no month available.
Pappas, S.P. "Photoinitiated Polymerization" Comph. Pol. Sci. 4 337-355 1989, no month available.
Kirilenko, G.V. et al. "An analog of the vesicular process with amplitude modulation of the incident light beam" Chemical Abstracts 111 569 [No. 111:12363 3 b] 1989, no month available.
Esrom et al. "UV excimer laser-induced pre-nucleation of surfaces followed by electroless metallization" Chemtronics 4 216-223 1989, no month available.
Esrom et al., "VUV light-induced depostion of palladium using an incoherent Xe2* excimer source" Chemtronics 4 1989, no month available.
Esrom et al. "UV Light-Induced Deposition of Copper Films" C5-719--C5-725 1989, no month available.
Falbe et al. Rompp Chemie Lexikon 9 270 1989, no month available.
Allen, Norman S. Photopolymerisation and Photoimaging Science and Technology pp. 188-199; 210-239 1989, no month available.
Derwent Publications, Ltd., London, SU 1423656 (Kherson Ind Inst), Sep. 15, 1988 (Abstract).
Derwent Publications, Ltd., London, EP 0280653 (Ciba GeigyAG), Aug. 31, 1988 (Abstract).
Abstract of patent, JP 63-190815 1988, no month available.
Patent Abstracts of Japan, JP 63179985 (Tomoegawa Paper Co. Ltd.), Jul. 23, 1988.
Derwent World Patents Index, JP 63179977 (Tomoegawa Paper Mfg Co Ltd), Jul. 23, 1988.
Furcone, S.Y. et al. "Spin-on B14Sr3Ca3Cy4O16+x superconducting thin films from citrate precursors," Appl. Phys. Lett. 52(25) 2180-2182 1988, no month available.
Abstract of patent, JP 63-144329 1988, no month available.
Abstract of patent, JP 63-130164 1988, no month available.
Derwent Publications, Ltd., London, J6 3112770 (Toray Ind Inc), May 17, 1988 (Abstract).
Derwent Publications, Ltd., London, J6 3108074 (Konishiroku Photo KK), May 12, 1988, (Abstract).
Derwent Publications, Ltd., London, London,J6 3108073 (Konishiroku Photo KK), May 12, 1988 (Abstract).
Abstract of patent, JP 61-77846 1988, no month available.
Abstract of patent, JP 63-73241 1988, no month available.
Abstract of patent, JP 6347762, 1988, no month available.
Abstract of patent, JP 63-47763, 1988, no month available.
Abstract of patent, JP 63-47764, 1988, no month available.
Abstract of patent, JP 63-47765, 1988, no month available.
Eliasson, B., et al. "UV Excimer Radiation from Dielectric-Barrier Discharges" Applied Physics B 46 299-303 1988, no month available.
Eliasson et al. "New Trends in High Intensity UV Generation" EPA Newsletter (32) 29-40 1988, no month available.
Cotton, F.A. "Oxygen: Group Via(16)" Advanced Inorganic Chemistry 5th ed. 473-474 1988, no month available.
Derwent Publications, Ltd., London, J6 2270665 (Konishiroku Photo KK), Nov. 25, 1987 (Abstract).
Abstract of patent, JP 62-215261 1987, no month available.
Database WPI, Derwent Publications Ltd., London, JP 62032082 (Mitsubishi Denki KK), Feb. 12, 1987. (Abstract).
Abstract of patent, JP 62-32082 1987, no month available.
Derwent Publications Ltd., London, J6 2007772 (Alps Electric KK.), Jan. 14, 1987 (Abstract).
Gross et al. "Laser direct-write metallization in thin palladium acetate films" J. App. Phys. 61 (4) 1628-1632 1987, no month available.
Al-Ismail et al. "Some experimental results on thin polypropylene films loaded with finely-dispersed copper" Journal of Materials Science 415-418 1987, no month available.
Baufay et al. "Optical self-regulation during laser-induced oxidation of copper" J. Appl. Phys 61 (9) 4640-4651 1987, no month available.
Derwent Publications Ltd., London, JA 0284478 (Sanyo Chem Ind Ltd.), Dec. 15 1986 (Abstract).
Abstract of patent, JP 61251842 1986, no month available.
Database WPI, Derwent Publications Ltd., London, GB; SU, A, 1098210 (Kutulya L A) Jun. 23, 1986.
Abstract of patent, JP 61-97025 1986, no month available.
Abstract of patent, JP 61-87760 1986, no month available.
Derwent Publications Ltd., London, DL 0234731 (Karl Marx Univ. Leipzig), Apr. 9, 1986. (Abstract).
Derwent World Patents Index, SU 1219612 (AS USSR Non-AQ SOLN) Mar. 23, 1986.
Derwent Publications, Ltd., London, J6 1041381 (Osaka Prefecture), Feb. 27, 1986 (Abstract).
Dialog, JAPIO, JP 61-034057 (Ciba Geigy AG) Feb. 18, 1986.
Derwent World Patents Index, JP 61027288 (summitomo Chem Ind KK) Feb. 6, 1986.
Sakai et al. "A Novel and Practical Synthetic Method of 3(2H)-Furanone Derivatives," J. Heterocyclie Chem. 23 pp. 1199-1201 1986, no month available.
Jellinek, H.H.G. et al. "Evolution of H2O and CO2 During the Copper-Catalyzed Oxidation of Isotactic Polypropylene," J. Polymer Sci. 24 389-403 1986, no month available.
Jellinke, H.H.G. et al. "Diffusion of Ca2+ Catalysts from Cu-Metal Polymer or Cu-Oxide/Polymer Interfaces into Isotactic Polypropylene," J. Polymer Sci. 24 503-510 1986, no month available.
John J. Eisch and Ramiro Sanchez "Selective, Oxophilic Ketones with Bis (dichloraluminum) Phenylimide" J. Org. Chem. 51 (10) 1848-1852 1986, no month available.
Derwent Publications Ltd., London, J6 0226575 (Sumitomo Chem Ind Ltd.), Oct. 11, 1985 (Abstract).
Abstract of patent JP 60-156761 1985, no month available.
Derwent Publications Ltd., London, J,A, 0011415 (Fugi Photo Film KK), Jan. 21, 1985. (Abstract).
Derwent Publications Ltd., London J6 0011-449-A (Taoka Chemical KK) Jan. 21, 1985 (abstract).
Roos, G. et al. "Textile applications of photocrosslinkable polymers" Chemical Abstracts 103 57 [No. 103:23690j] 1985, no month available.
Derwent World Patents Index, EP 127574 (Ciba Geigy AG), Dec. 5, 1984.
Derwent Publications Ltd., London, JP 0198187 (Canon KK), Nov. 9, 1984. (Abstract).
Derwent Publications Ltd., London, J,A, 0169883 (Ricoh KK), Sep. 25, 1984. (Abstract).
Derwent Publications Ltd., London, JA 0169883 (Ricoh KK), Sep. 25, 1984 (Abstract).
Derwent Publications Ltd., London, JA 0198187 (Canon KK), Sep. 11, 1984 (Abstract).
Derwent Publications Ltd., London, J,A, 0053563 (Dainippon Toryo KK), Mar. 28, 1984. (Abstract).
Derwent Publications Ltd., London, J,A, 0053562 (Dainippon Toryo KK), Mar. 28, 1984. (Abstract).
Abstract of Patent, JA 0053563 (Dainippon Toryo KK), Mar. 28, 1984 (Abstract).
Abstract of Patent, JA 0053562 (Dainippon Toryo KK), Mar. 28, 1984 (Abstract).
Derwent Publications Ltd., London, J,A, 0051961 (Dainippon Toryo KK), Mar. 26, 1984. (Abstract).
Abstract of Patent JA 0051961 (Dainippon Toryo KK), Mar. 26, 1984 (Abstract).
Saenger, W. "Structural Aspects of Cyclodextrins and Their Inclusion Complexes" Inclusion Compounds--Structural Aspects of Inclusion Compounds formed by Organic Host 2 231-259 1984, no month available.
Szejtli "Industrial Applications of Cyclodextrins" Inclusion Compounds: Physical Prop. & Applns 3 331-390 1984, no month available.
Kano et al. "Three-Component Complexes of Cyclodextrins. Exciplex Formation in Cyclodextrin Cavity," J. Inclusion Phenomena 2 pp. 737-746 1984, no month available.
Suzuki et al. "Spectroscopic Investigation of Cyclodextrin Monomers, Derivatives, Polymers and Azo Dyes," J. Inclusion Phenomena 2, pp. 715-724 1984, no month available.
Abstract of Patent, JA 0222164 (Ricoh KK), Dec. 23, 1983 (Abstract).
Abstract of patent, JP 58211426 (Sekisui Plastics KK), (Dec. 8, 1983).
Derwent Publications, Ltd., London, EP 0072775 (Ciba Geigy AG), Feb. 23, 1983 (Abstract).
van Beek, H.C.A "Light-Induced Colour Changes in Dyes and Materials" Color Res. and Appl. 8 176-181 1983, no month available.
Connors, K.A. "Application of a stoichiometric model of cyclodextrin complex formation" Chemical Abstracts 98 598 [No. 98:53067g] 1983, no month available.
Abstract of Patent, EP 0065617 (IBM Corp.), Dec. 1, 1982 (Abstract).
Derwent Publications Ltd., London, J,A, 0187289 (Honshu Paper Mfg KK), Dec. 17, 1982. (Abstract).
Abstract of Patent, JA 0187289 (Honsho Paper Mfg KK), Dec. 17, 1982 (Abstract).
Abstract of Patent, JA 0185364 (Ricoh KK), Nov. 15, 1982 (Abstract).
Derwent Publications, Ltd., London J5 7139-146 (Showa Kako KK) Aug. 27, 1982(abstract).
Abstract of Patent, JA 0090069 (Canon KK), Jun. 4, 1982, (Abstract).
Derwent Publications, Ltd., London, JA 0061785 (Nippon Senka KK), Apr. 14, 1982 (Abstract).
Fischer, "Submicroscopic contact imaging with visible light by energy transfer" Appl. Phys. Letter 40(3) 1982, no month available.
Abstract of Patent, JA 0010659 (Canon KK), Jan. 2, 1982 (Abstract).
Abstract of Patent, JA 0010661 (Canon KK), Jan. 2, 1982 (Abstract).
Christen "Carbonylverbindungen: Aldehyde und Ketone," Grundlagen der Organischen Chemie 255 1982, no month available.
Derwent Publications Ltd., London, J,A, 0155263 (Canon KK), Dec. 1, 1981. (Abstract).
Abstract of Patent, JA 0155263 (Canon KK), Dec. 1, 1981 (Abstract).
Abstract of Patent, JA 0147861 (Canon KK), Nov. 17, 1981 (Abstract).
Derwent Publications Ltd., London, J,A 0143273 (Canon KK), Nov. 7, 1981. (Abstract).
Abstract of Patent, JA 0143272 (Canon KK), Nov. 7, 1981 (Abstract).
Abstract of Patent, JA 0136861 (Canon KK), Oct. 26, 1981 (Abstract).
Abstract of Patent, JA 6133378 (Canon KK), Oct. 19, 1981 (Abstract).
Abstract of Patent, JA 6133377 (Canon KK), Oct. 19, 1981 (Abstract).
Abstract of Patent, JA 6093775 (Canon KK), Jul. 29, 1981 (Abstract).
Derwent Publications Ltd., London, J,A, 0008135 (Ricoh KK), Jan. 27, 1981. (Abstract).
Derwent Publications Ltd., London, J,A, 0004488 (Canon KK), Jan. 17, 1981. (Abstract).
Abstract of Patent, JA 0004488 (Canon KK), Jan. 17, 1981 (Abstract).
Kirk-Othmer "Metallic Coatings," Encyclopedia of Chemical Technology 15 241-274 1981, no month available.
Komiyama et al. "One-Pot Preparation of 4-Hydroxychalcone .beta.-Cyclodextrin as Catalyst," Makromol. Chem. 2 733-734 1981, no month available.
Derwent Publications, Ltd., London CA 1086-719 (Sherwood Medical) Sep. 30, 1980 (abstract).
Derwent Publications Ltd., Database WPI, JP 55 113036 (Ricoh KK), Sep. 1, 1980.
Rosanske et al. "Stoichiometric Model of Cyclodextrin Complex Formation" Journal of Pharmaceutical Sciences 69 (5) 564-567 1980, no month available.
Semple et al. "Synthesis of Functionalized Tetrahydrofurans," Tetrahedron Letters 81 pp. 4561-4564 1980, no month available.
Kirk-Othmer "Film Deposition Techniques," Encyclopedia of Chemical Technology 10 247-283 1980, no month available.
Derwent World Patents Index, Derwent Info. Ltd., JP 54158941 (Toyo Pulp KK), Dec. 15, 1979. (Abstract).
Derwent World Patents Index, JP 54117536 (Kawashima F) Sep. 12, 1979.
Derwent Publications Ltd., London, J,A, 0005422 (Fuji Photo Film KK), Jan. 16, 1979. (Abstract).
Drexhage et al., "Photo-bleachable dyes and processes" Research Disclosure 85-87 1979, no month available.
"Color imaging devices and color filter arrays using photo-bleachable dyes" Research Disclosure 22-23 1979, no month available.
Wolffe, N.E., et al. "Electrophotography" Kirk-Othmer Encyclopedia of Chemical Technology 8 794-826 1979, no month available.
Derwent Publications Ltd., London, J,A, 0012037 (Pentel KK), Jan. 29, 1977. (Abstract).
Abstract of Patent, JA 0012037 (Pentel KK), Jan. 29, 1977 (Abstract).
Jenkins, P.W. et al., "Photobleachable dye material" Research Disclosure 18 [No. 12932] 1975, no month available.
Lamberts, R.L. "Recording color grid patterns with lenticules" Research Disclosure 18-19 [No. 12923] 1975, no month available.
Karmanova, L.S. et al. "Light stabilizers of daytime fluorescent paints" Chemical Abstracts 82 147 [No. 59971p] 1975, no month available.
Prokopovich, B. et al. "Selection of effective photoinducers for rapid hardening of polyester varnish PE-250" Chemical Abstracts 83 131 [No. 81334a] 1975, no month available.
"Variable Contrast Printing System" Research Disclosure 19 [No. 12931] 1975, no month available.
Lakshman "Electronic Absorption Spectrum of Copper Formate Tetrahydrate" Chemical Physics Letters 31 (2) 331-334 1975, no month available.
Derwent Publications, Ltd., London J4 9131-226 (TNational Cash Register C) Dec. 16, 1974 (abstract).
Chang, I.F., et al. "Color Modulated Dye Ink Jet Printer" IBM Technical Disclosure Bulletin 17(5) 1520-1521 1974, no month available.
"Darocur 1173: Liquid Photoiniator for Ultraviolet Curing of Coatings" 1974.
Hosokawa et al. "Ascofuranone, an antibiotic from Asochyta," Japan Kokai 73 91,278 (Nov. 28, 1973) Merck Index 80 p. 283; abstract 94259t 1974, no month available.
Abstract of patent, NL 7112489 (Dec. 27, 1971).
Gafney et al. "Photochemical Reactions of Copper (II)--1,3-Diketonate Complexes" Journal of the Americqal Chemical Society 1971, no month available.
Derwent Publications, Ltd., London SU 292698-S Jan. 15, 1971 (abstract).
Derwent World Patents Index,CS 120380 (Kocourek, Jan) Oct. 15, 1966.
Rigdon, J.E. "In Search of Paper that Spies Can't Copy" Wall Street Journal, no date available.
Chatterjee,S. et al. "Photochemistry of Carbocyanine Alkyltriphenylborate Salts: Intra-Ion-Pair Electron Transfer and the Chemistry of Boranyl Radicals" J. Am. Chem. Soc. 112 6329-6338, no date available.
"Assay--Physical and Chemical Analysis of Complexes" AMAIZO, no date available.
"Cyclodextrin" AMAIZO, no date available.
"Beta Cyclodextrin Polymer (BCDP)" AMAIZO, no date available.
"Chemically Modified Cyclodextrins" AMAIZO, no date available.
"Cyclodextrin Complexation" American Maize Products Co., no date available.
"Monomers" Scientific Polymer Products Inc., no date available.
Suppan, Paul "Quenching of Excited States" Chemistry and Light 65-69, no date available.
Yamaguchi, H. et al. "Supersensitization. Aromatic ketones as supersensitizers" Chemical Abstracts 53 107 (d), no date available.
Stecher, H. "Ultraviolet-absorptive additives in adhesives, lacquers and plastics" Chemical Abstracts 53 14579 (c), no date available.
Maslennikov, A.S. "Coupling of diazonium salts with ketones" Chemical Abstracts 60 3128e, no date available.
Derwent Publications Ltd., London, 4 9128022 no date available.
Abstract of Patent, JP 405195450, no date available.
Rose, Philip I. "Gelatin," Encyclopedia of Chemical Technology 7 488-513, no date available.

Colorants and colorant modifiers

Information

Patent Number

Date Filed

Date Issued

Inventors

Original Assignees

Examiners

Agents

CPC

US Classifications

Field of Search

US

International Classifications