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

2

, O

3

, SO

2

, and NO

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:

which efficiently absorbs radiation having a wavelength at about 308 nanometers, or

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 (see co-pending U.S. patent application Ser. No. 08/359,670). 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. The data processing forms of the present invention are disclosed in co-pending U.S. patent application Ser. No. 08/360,501, which is incorporated herein by reference.

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 184 (1-hydroxycyclohexyl phenyl ketone), and the molecular includant is β-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 184 (1-hydroxycyclohexyl phenyl ketone), and the molecular includant is β-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:

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 artificial 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 β-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-mercaptomerthlypropionyl)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-toluenesulfonates (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° C. to around ambient temperature, i.e., to 20°-25° 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-(dimethylamnino)-α-[4-(dimethylamino)phenyl]-α-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 β-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-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

29

,N

30

,N

31

,N

32

]copper}; carotenoid dyes, such as trans-β-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 impoved 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, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, sulfated β-cyclodextrin, hydroxyethyl α cyclodextrin, carboxymethyle α cyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γ cyclodextrin, octyl succinated α cyclodextrin, octyl succinated β cyclodextrin, octyl succinated γ cyclodextrin and sulfated β and γ-cyclodextrin (American Maize-Products Company, Hammond, Ind.).

The desired molecular includant is α-cyclodextrin. More particularly, in some embodiments, the molecular includant is an α-cyclodextrin. In other embodiments, the molecular includant is a β-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 β-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 β-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 184, and the molecular includant is β-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 184, and the molecular includant is β-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

2

). The power density level range is between approximately 5 mW/cm

2

and 15 mW/cm

2

, more particularly 8 to 10 mW/cm

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 Haräus 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 crtical 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 651, Ciba-Geigy Corporation, Hawthorne, N.Y.); 1-hydroxycyclohexyl phenyl ketone (IRGACURE 500); 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one] (IRGACURE 907); 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (IRGACURE 369); and 1-hydroxycyclohexyl phenyl ketone (IRGACURE 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 KI85, Ciba-Geigy Corporation, Hawthorne, New York); Cyracure 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 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:

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:

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 wavelenth selective sensitizer may be used to stabilize a colorant. An example of a photoreactor that is modified according to the present invention is IRGACURE® 2959. The unmodified IRGACURE® 2959 and the dehydrated IRGACURE® 2959 are shown below.

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 184, Ciba-Geigy); α,α-dimethoxy-α-hydroxy acetophenone (DAROCUR 1173, Merck); 1-(4-Isopropylphenyl)-2-hydroxy-2-methyl-propan-1-one (DAROCUR 1116, Merck); 1-[4-(2-Hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propan-1-one (IRGACURE® 2959, Merck); Poly[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] propan-1-one ] (ESACURE KIP, Fratelli Lamberti); Benzoin (2-Hydroxy-1,2-diphenylethanone) (ESACURE BO, Fratelli Lamberti); Benzoin ethyl ether (2-Ethoxy-1,2-diphenylethanone) (DAITOCURE EE, Siber Hegner); Benzoin isopropyl ether (2-Isopropoxy-1,2-diphenylethanone) (VICURE 30, Stauffer); Benzoin n-butyl ether (2-Butoxy-1,2-diphenylethanone) (ESACURE EBI, Fratelli Lamberti); mixture of benzoin butyl ethers (TRIGONAL 14, Akzo); Benzoin iso-butyl ether (2-Isobutoxy-1,2-diphenylethanone) (VICURE 10, Stauffer); blend of benzoin n-butyl ether and benzoin isobutyl ether (ESACURE EB3, ESACURE EB4, Fratelli Lamberti); Benzildimethyl ketal (2,2-Dimethoxy-1,2-diphenylethanone) (“BDK”) (IRGACURE 651, Ciba-Geigy); 2,2-Diethoxy-1,2-diphenylethanone (UVATONE 8302, Upjohn); α,α-Diethoxyacetophenone (2,2-Diethoxy-1-phenyl-ethanone) (“DEAP”, Upjohn), (DEAP, Rahn); and α,α-Di-(n-butoxy)-acetophenone (2,2-Dibutoxyl-1-phenylethanone) (UVATONE 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:

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

2

. It is to be understood that other transition metal salts can be used in performing the Nohr-MacDonald elimination reaction but ZnCl

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:

wherein

R

1

is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;

R

2

is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;

R

3

is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group; and

R

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° C. and 150° C. A suitable temperature for dehydrating phthaloylglycine-2959 is approximately 124° 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:

In another embodiment, as shown below, only the modified IRGACURE® 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® 2959 can be used in the present invention.

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:

Another stabilizer that is considered part of the present invention is an arylketoalkene having the following general formula:

wherein if R

1

is an aryl group, then R

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

2

is an aryl group, then R

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.

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

1

and R

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

1

or R

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:

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

1

, or R

2

, or both R

1

and R

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

1

, or R

2

, or both R

1

and R

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:

Another desirable arylketoalkene stabilizing compound has the following formula:

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:

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═O)—). However, the linkage may include, but is not limited to, a ketone linkage (—(C═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:

Yet another desirable arylketoalkene stabilizing compound with a ketone linkage has the following formula:

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(ε-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-1,4phenyleneisopropylidene-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-1,4phenylene), 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-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 β-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 184, Ciba-Geigy Corporation, Hawthorne, New York), 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° 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° 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 β-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° C. and 0.5 ml of triethylamine added. The reaction mixture was maintained at 50° C. for an hour and allowed to cool to ambient temperature. In this preparation, no attempt was made to isolate the product, a β-cyclodextrin to which an ultraviolet radiation transorber had been covalently coupled (referred to hereinafter for convenience as β-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® 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 β-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 oxlate (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 β-cyclodextrin-transorber Colorant A inclusion complex moved down the column first, cleanly separating from both free Colorant A and β-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 β-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° 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

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 β-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 β-cyclodextrin in N,N-dimethylformamide 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 β-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

Decolorization

Solvent

Solubility

Time

N,N-Dimethylformamide

Poor

1

minute

Dimethylsulfoxide

Soluble

<10

seconds

Acetone

Soluble

<10

seconds

Hexane

Insoluble

—

Ethyl Acetate

Poor

1

minute

Finally, 10 mg of the β-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 β-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 β-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, β-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 β-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° C. and 0.5 ml of triethylamine added. The reaction mixture was maintained at 50° 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 β-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 β-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® 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° C. The reaction is summarized as follows:

The resulting product, designated phthaloylglycine-2959, had the following physical parameters:

IR [NUJOL MULL] ν

max

3440, 1760, 1740, 1680, 1600 cm−1

1H NMR [CDCl3] ∂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:

The resulting reaction product had the following physical parameters:

IR (NUJOL) ν

max

1617 cm−1 (C═C—C═O)

EXAMPLE 5

This example describes the Nohr-MacDonald elimination reaction used to dehydrate the phthaloylglycine-2959 produced in Example 5 .

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:

The resulting reaction product had the following physical parameters:

Melting Point: 138° C. to 140° C.

Mass spectrum: m/e: 393 M+, 352, 326, 232, 160.

IR (KB)ν

max

1758, 1708, 1677, 1600 cm−1

1H NMR [DMSO] ∂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] ∂ppm 65.9 (CH2═)

EXAMPLE 6

This example describes a method of producing a β-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) β-cyclodextrin (American Maize Product Company, Hammond, Ind.) (designated β-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 β-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.

The β-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 β-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 β-cyclodextrin having a dehydrated phthaloylglycine-2959 group; and 50 ml of water. The water was heated to 70° 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° 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 ν

max

610 nm (cf cv ν

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 (0.1mole) 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® 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° C. The reaction is summarized in the following reaction:

The resulting reaction product had the following physical parameters:

IR [NUJOL MULL] ν

max

3460, 1760, 1700, 1620, 1600 cm−1

1H [CDC13] ∂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 β-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:

and dehydrated phthaloylglycine-2959, represented by the following formula::

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 analyses. 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

Fade

Blue BO

Time

Phthaloylglycine-2959

3 parts by weight

1 part by weight

2

min

10 parts by weight

1 part by weight

1½

min

20 parts by weight

1 part by weight

30

sec

Dehydrated

Phthaloylglycine-2959

3parts by weight

1 part by weight

4

min

10 parts by weight

1 part by weight

8

min

20 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 dwascharge 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 dwascharge 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:

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 cwerefully 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 analyses. 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 Pure

Compound

Blue

Fade Time

20 parts 2959 (Hydroxy)

1 part

<2 min

20 parts 2959 (Dehydroxy)

1 part

<2 min

None

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 β-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 β-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 β-cyclodextrin at a concentration of 20 mg/ml in acetonitrile.

3. The Victoria Pure Blue BO included in β-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

a

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 β-cyclodextrin was capable of stabilizing the dye under the mercury discharge light.

EXAMPLE 12

Preparation of Epeoxide Intermediate of Dehydrated Phthaloylglycine-2959

The epoxide intermediate of dehydrated phthaloylglycine 2959 was prepared according to the following reaction:

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 15-20° 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 15-20° C. This step took about 4 minutes. The mixture was then stirred for 3 hours at about 20-25° 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

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:

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 (0.031 mol), 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° C. to 5° 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° 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° 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° 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° 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:

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° 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° C. using a warm water bath and the H

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

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 (3×80 ml) with diethyl ether (Aldrich Chemical Co., Milwaukee, Wis.).

The organic layers were condensed and washed with water and dried with MgSO

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:

To a 100 ml round bottomed flask was placed 6.0 g β-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

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

101.8

2

72.9

3

72.3

4

81.4

5

71.9

6

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:

To a 250 ml round bottomed flask was added 10.0 g (4-8 mole) of tosylated substituted cyclodextrin, 20.7 g (4-8 mmol) of thiol (mercapto dehydrated phthaloylglycine 2959) in 100 ml of DMF. The reaction mixture was cooled to 0° 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° 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 β-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° 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 β-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° 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

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 Compositions

Composition

Decolorization Times (Seconds)

Example 18

1

Example 19

3-4

Example 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 β-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 β-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:

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

a

Hydroxy Compound

<20

sec

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 ground 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° 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 3×5 inches (7.6 cm×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® 500 (“UVRT A”), Irgacure® 651 (“UVRT B”), and Irgacure® 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® 1004F (Shell Oil Company, Houston, Tex.); a poly(ethylene glycol) having a weight-average molecular weight of about 8,000 (“Polymer B”), Carbowax 8000 (Aldrich Chemical Company); and a poly(ethylene glycol) having a weight-average molecular weight of about 4,600 (“Polymer C”), Carbowax 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 Containing

Colorant and Ultraviolet Radiation Transorber (“UVRT”)

Colorant

UVRT

Polymer

Film

Type

Parts

Type

Parts

Type

Parts

A

A

1

A

6

A

90

C

4

B

A

1

A

12

A

90

C

8

C

A

1

A

18

A

90

C

12

D

A

1

A

6

A

90

B

4

E

A

1

B

30

A

70

F

A

1

—

—

A

100

G

A

1

A

6

B

90

C

4

H

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° 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

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 Containing

Colorant and Ultraviolet Radiation Transorber (UVRT)

to Ultraviolet Radiation

Excimer Lamp

Film

Lamp A

Lamp B

Fusion Lamp

A

3

3

15

B

2

3

10

C

1

3

10

D

1

1

10

E

1

1

1

F

5

5

10

G

3

—

10

H

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° 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

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 (μW)

Reading (mW/cm

2

)

24.57

9.63

19.56

9.35

22.67

9.39

19.62

9.33

17.90

9.30

19.60

9.30

21.41

9.32

17.91

9.30

23.49

9.30

19.15

9.36

17.12

9.35

21.44

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° 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

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 (μW)

Reading (mW/cm

2

)

23.46

9.32

16.12

9.31

17.39

9.32

20.19

9.31

16.45

9.29

20.42

9.31

18.33

9.32

15.50

9.30

20.90

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° C. The power density at the lamp's outer surface typically is in the range from about 4 to about 20 joules per square meter (J/m

2

).

Table 12 summarizes the intensity readings which were obtained by a meter located on the surface of the substrate at position 1 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

Reading

Distance (cm)

Background (μW)

(mW/cm

2

)

5.5

18.85

9.30

6.0

15.78

9.32

10

18.60

9.32

15

20.90

9.38

20

21.67

9.48

25

19.86

9.69

30

22.50

11.14

35

26.28

9.10

40

24.71

7.58

50

26.95

5.20

EXAMPLE 28

This example describes a method of making the following wavelength-selective sensitizer:

The wavelength-selective sensitizer is synthesized as summarized below:

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° 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

+

) 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:

To a 250 ml round bottom flask fitted with a magnetic stir bar, condensor, 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

6

) δ2.80[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:

The wavelength-selective sensitizer is synthesized as summarized below:

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 (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

+

), 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:

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° 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® 2959, as is summarized below:

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® 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

+

), 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 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° C. ), using a #3 drawdown bar. A similar sample was made with only 1% Victoria Pure Blue BO in 99% carbowax.

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 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 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=no change.

TABLE 13

Irradiation

Time (Hour)

Control Sheet

Test Sheet

0

NC

NC

1

5-10%

NC

2

10-15%

NC

3

20%

NC

4

30%

NC

5

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:

The wavelength-selective sensitizer is synthesized as summarized below:

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

+

), 245, 218, 193, 179, 151, 125, 73.

A 250 ml round bottom flask is fitted with a Dean and Stark adaptor and condensor. 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:

The wavelength-selective sensitizer is synthesized as summarized below:

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

+

), 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:

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:

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:

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

Compound

Produced 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 × 10

−4

2.4 × 10

−4

2.9 × 10

−4

mole

mole

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 Percent

Fade Results

Compound

# of Pages

% Fade of

% Fade of

Produced in:

Concentration

Generated

Sheet #50

Sheet #100

Control

200

80-90

80-90

Example 29

1.2 × 10

−4

mole

195

N/C

N/C

(5%)

Example 40

1.2 × 10

−4

mole

194

10-15

10-15

(6.6%)

Example 41

1.2 × 10

−4

mole

194

10-15

10-15

(6.2%)

Example 29

2.4 × 10

−4

mole

196

N/C

N/C

(10%)

Example 40

2.4 × 10

−4

mole

194

5-10

5-10

(13.2%)

Example 41

2.4 × 10

−4

mole

195

5-10

5-10

(12.4%)

Example 29

2.9 × 10

−4

mole

198

N/C

N/C

(12%)

Example 40

2.9 × 10

−4

mole

196

5-10

5-10

(16%)

Example 41

2.9 × 10

−4

mole

197

5-10

5-10

(15%)

TABLE 16

Epson Stylus Color Printer (Model EscP2) Percent Fade

Results

Compound

# of Pages

% Fade of

% Fade of

Produced in:

Concentration

Generated

Sheet #50

Sheet #100

Control

153

80-90

80-90

Example 29

1.2 × 10

−4

mole

152

N/C

N/C

(5%)

Example 40

1.2 × 10

−4

mole

153

10-15

10-15

(6.6%)

Example 41

1.2 × 10

−4

mole

154

10-15

10-15

(6.2%)

Example 29

2.4 × 10

−4

mole

150

N/C

N/C

(10%)

Example 40

2.4 × 10

−4

mole

152

5-10

5-10

(13%)

Example 41

2.4 × 10

−4

mole

151

5-10

5-10

(12%)

Example 29

2.9 × 10

−4

mole

152

N/C

N/C

(12%)

Example 40

2.9 × 10

−4

mole

150

5-10

5-10

(16%)

Example 41

2.9 × 10

−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 substrate having thereon or therein a molecular includant and at least one ultraviolet radiation transorber.
2. The substrate of claim 1, wherein the molecular includant comprises a clathrate, an intercalate, a zeolite, or a cyclodextrin.
3. The substrate of claim 1, wherein the molecular includant comprises a cyclodextrin.
4. The substrate of claim 1, wherein the molecular includant comprises α-cyclodextrin, β-cyclodextrin, γ-cyclodcxtrin, δ-cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α-cyclodextrin, carboxymethyl α-cyclodextrin, carboxymethyl β-cyclodextrin carboxymethyl γ-cyclodextrin, octyl succinated α-cyclodextrin, octyl succinated β-cyclodextrin, octyl succinated γ-cyclodextrin, sulfated β-cyclodextrin, sulfated γ-cyclodextrin, hydroxyethyl γ-cyclodextrin, hydroxyisopropyl γ-cyclodextrin, hydroxypropyl γ-cyclodextrin, octyl succinate γ-cyclodextrin, carboxymethyl γ-cyclodextrin, or a combination thereof.
5. The substrate of claim 4, wherein the molecular includant is an α-cyclodextrin or a β-cyclodextrin.
6. The substrate of claim 1, wherein the molecular includant is covalently bonded to the at least one ultraviolet radiation transorber.
7. The substrate of claim 1, wherein the substrate further comprises a colorant.
8. The substrate of claim 7, wherein the colorant is at least partially included within a cavity of the molecular includant.
9. The substrate of claim 1, wherein the substrate is paper, a woven web, a nonwoven web, a film, or a combination thereof.
10. The substrate of claim 1, wherein the substrate is paper.
11. A method of making a substrate comprising the steps of:providing a substrate; providing a composition comprising a molecular includant and at least one ultraviolet radiation transorber; and incorporating the composition into or onto the substrate.
12. The method of claim 11, wherein the molecular includant comprises a clathrate, an intercalate, a zeolite or a cyclodextrin.
13. The method of claim 12, wherein the cyclodextrin is α-cyclodextrin, β-cyclodextrin, gamma-cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, sulfonated β-cyclodextrin or sulfonated gamma-cyclodextrin.
14. The method of claim 11, wherein the substrate comprises paper, a woven fabric, a nonwoven web, a film, or a combination thereof.
15. The method of claim 11, wherein the substrate comprises paper.
16. The method of claim 11, wherein the composition is in the substrate.
17. The method of claim 11, wherein the composition further comprises a polymeric carrier and is present as a toner.
18. A substrate formed from the method of claim 11.
19. A substrate having thereon or therein a colored composition comprising:a colorant; a molecular includant; and at least one ultraviolet radiation transorber.
20. The substrate of claim 19, wherein the molecular includant comprises a clathrate, an intercalate, a zeolite or a cyclodextrin.
21. The substrate of claim 19, wherein the molecular includant is α-cyclodextrin, β-cyclodextrin, gamma-cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, sulfonated β-cyclodextrin, sulfonated gamma-cyclodextrin, or a combination thereof.
22. The substrate of claim 19, wherein the substrate comprises paper, a woven fabric, a nonwoven web, a film, or a combination thereof.
23. The substrate of claim 19, wherein the substrate comprises paper.
24. The substrate of claim 19, wherein the colored composition is in the substrate.
25. The substrate of claim 19, wherein the colored composition further comprises a polymeric carrier and is present as a toner.
26. The substrate of claim 19, wherein the colorant is selected from the group consisting triaryl methyl dyes, monoazo dyes, thiazine dyes, oxazine dyes, naphthalimide dyes, azine dyes, cyanine dyes, indigo dyes, coumarin dyes, benimidazole dyes, paraquinoidal dyes, fluorescein dyes, diazonium salt dyes, azoic diazo dyes, phenylenediamine dyes, disazo dyes, anthraquinone dyes, trisazo dyes, xanthene dyes, proflavine dyes, sulfonaphthalein dyes, phthalocyanien dyes, carotenoid dyes, carminic acid dyes, avure dyes, and acridine dyes.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional application of U.S. patent application Ser. No. 08/983,159, filed on Dec. 29, 1997, now U.S. Pat. No. 6,033,465, which is a national phase application of International Application PCT/US96/04689, filed on Apr. 5, 1996, which claims the benefit of priority to U.S. Provisional Patent Application Ser. No. 60/000,570, filed on Jun. 28, 1995, which is a continuation-in-part of U.S. patent application Ser. No. 08/461,372, filed on Jun. 5, 1995, 1995, now abandoned, which is a continuation-in-part of U.S. patent application Ser. No. 08/403,240, filed on Mar. 10, 1995, now abandoned, which is a continuation-in-part of U.S. patent application Ser. No. 08/373,958, filed on Jan. 17, 1995, now abandoned, which is a continuation-in-part of U.S. patent application Ser. No. 08/359,670, filed Dec. 20, 1994, now abandoned, and U.S. patent application Ser. No. 08/360,501, filed Dec. 21, 1994, now U.S. Pat. No. 5,865,471, which are continuations-in-part of U.S. patent application Ser. No. 08/258,858, filed on Jun. 13, 1994, now abandoned, which is a continuation-in-part of U.S. patent application Ser. No. 08/183,683, filed on Jan. 19, 1994, and U.S. patent application Ser. No. 08/119,912, filed Sep. 10, 1993, both now abandoned;

US Referenced Citations (666)

Number	Name	Date	Kind
575228	von Gallois	Jan 1897	A
582853	Feer	May 1897	A
893636	Maywald	Jul 1908	A
1013544	Fuerth	Jan 1912	A
1325971	Akashi	Dec 1919	A
1364406	Olsen	Jan 1921	A
1436856	Brenizer et al.	Nov 1922	A
1744149	Staehlin	Jan 1930	A
1803906	Krieger et al.	May 1931	A
1844199	Bicknell et al.	Feb 1932	A
1876880	Drapal	Sep 1932	A
1880572	Wendt et al.	Oct 1932	A
1880573	Wendt et al.	Oct 1932	A
1916350	Wendt et al.	Jul 1933	A
1916779	Wendt et al.	Jul 1933	A
1955898	Wendt et al.	Apr 1934	A
1962111	Bamberger	Jun 1934	A
2005378	Kiel	Jun 1935	A
2005511	Stoll et al.	Jun 1935	A
2049005	Gaspar	Jul 1936	A
2054390	Rust et al.	Sep 1936	A
2058489	Murch et al.	Oct 1936	A
2062304	Gaspar	Dec 1936	A
2090511	Crossley et al.	Aug 1937	A
2097119	Eggert	Oct 1937	A
2106539	Schnitzspahn	Jan 1938	A
2111692	Saunders et al.	Mar 1938	A
2125015	Gaspar	Jul 1938	A
2130572	Wendt	Sep 1938	A
2132154	Gaspar	Oct 1938	A
2145960	Wheatley et al.	Feb 1939	A
2154996	Rawling	Apr 1939	A
2159280	Mannes et al.	May 1939	A
2171976	Erickson	Sep 1939	A
2181800	Crossley et al.	Nov 1939	A
2185153	Lecher et al.	Dec 1939	A
2220178	Schneider	Nov 1940	A
2230590	Eggert et al.	Feb 1941	A
2237885	Markush et al.	Apr 1941	A
2243630	Houk et al.	May 1941	A
2268324	Polgar	Dec 1941	A
2281895	van Poser et al.	May 1942	A
2328166	Poigar et al.	Aug 1943	A
2346090	Staehle	Apr 1944	A
2349090	Haddock	May 1944	A
2356618	Rossander et al.	Aug 1944	A
2361301	Libby, Jr. et al.	Oct 1944	A
2364359	Kienle et al.	Dec 1944	A
2381145	von Glahn et al.	Aug 1945	A
2382904	Federsen	Aug 1945	A
2386646	Adams et al.	Oct 1945	A
2402106	von Glahn et al.	Jun 1946	A
2416145	Biro	Feb 1947	A
2477165	Bergstrom	Jul 1949	A
2527347	Bergstrom	Oct 1950	A
2580461	Pearl	Jan 1952	A
2601669	Tullsen	Jun 1952	A
2612494	von Glahn et al.	Sep 1952	A
2612495	von Glahn et al.	Sep 1952	A
2628959	von Glahn et al.	Feb 1953	A
2647080	Joyce	Jul 1953	A
2680685	Ratchford	Jun 1954	A
2728784	Tholstrup et al.	Dec 1955	A
2732301	Robertson et al.	Jan 1956	A
2744103	Koch	May 1956	A
2757090	Meugebauer et al.	Jul 1956	A
2763550	Lovick	Sep 1956	A
2768171	Clarke et al.	Oct 1956	A
2773056	Helfaer	Dec 1956	A
2798000	Monterman	Jul 1957	A
2809189	Stanley et al.	Oct 1957	A
2827358	Kaplan et al.	Mar 1958	A
2834773	Scalera et al.	May 1958	A
2875045	Lurie	Feb 1959	A
2892865	Giraldi et al.	Jun 1959	A
2897187	Koch	Jul 1959	A
2936241	Sharp et al.	May 1960	A
2940853	Sagura et al.	Jun 1960	A
2955067	McBurney et al.	Oct 1960	A
2992129	Gauthier	Jul 1961	A
2992198	Funahashi	Jul 1961	A
3030208	Schellenberg et al.	Apr 1962	A
3071815	MacKinnon	Jan 1963	A
3075014	Palopoli et al.	Jan 1963	A
3076813	Sharp	Feb 1963	A
3104973	Sprague et al.	Sep 1963	A
3114634	Brown et al.	Dec 1963	A
3121632	Sprague et al.	Feb 1964	A
3123647	Duennenberger et al.	Mar 1964	A
3133049	Hertel et al.	May 1964	A
3140949	Sprague et al.	Jul 1964	A
3154416	Fidelman	Oct 1964	A
3155509	Roscow	Nov 1964	A
3175905	Wiesbaden	Mar 1965	A
3178285	Andreau et al.	Apr 1965	A
3238163	O'Neill	Mar 1966	A
3242215	Heitmiller	Mar 1966	A
3248337	Zirker et al.	Apr 1966	A
3266973	Crowley	Aug 1966	A
3282886	Gadecki	Nov 1966	A
3284205	Sprague et al.	Nov 1966	A
3300314	Rauner et al.	Jan 1967	A
3304297	Wegmann et al.	Feb 1967	A
3305361	Gaynor et al.	Feb 1967	A
3313797	Kissa	Apr 1967	A
3320080	Mazzarella et al.	May 1967	A
3330659	Wainer	Jul 1967	A
3341492	Champ et al.	Sep 1967	A
3359109	Harder et al.	Dec 1967	A
3361827	Biletch	Jan 1968	A
3363969	Brooks	Jan 1968	A
3382700	Willems et al.	May 1968	A
3397984	Williams et al.	Aug 1968	A
3415875	Luethi et al.	Dec 1968	A
3418118	Thommes et al.	Dec 1968	A
3445234	Cescon et al.	May 1969	A
3453258	Parmerter et al.	Jul 1969	A
3453259	Parmerter et al.	Jul 1969	A
3464841	Skofronick	Sep 1969	A
3467647	Benninga	Sep 1969	A
3479185	Chambers	Nov 1969	A
3502476	Kohei et al.	Mar 1970	A
3503744	Itano et al.	Mar 1970	A
3514597	Haes et al.	May 1970	A
3541142	Cragoe, Jr.	Nov 1970	A
3546161	Wolheim	Dec 1970	A
3547646	Hori et al.	Dec 1970	A
3549367	Chang et al.	Dec 1970	A
3553710	Lloyd et al.	Jan 1971	A
3563931	Horiguchi	Feb 1971	A
3565753	Yurkowitz	Feb 1971	A
3574624	Reynolds et al.	Apr 1971	A
3579533	Yalman	May 1971	A
3595655	Robinson et al.	Jul 1971	A
3595657	Robinson et al.	Jul 1971	A
3595658	Gerlach et al.	Jul 1971	A
3595659	Gerlach et al.	Jul 1971	A
3607639	Krefeld et al.	Sep 1971	A
3607693	Heine et al.	Sep 1971	A
3607863	Dosch	Sep 1971	A
3615562	Harrison et al.	Oct 1971	A
3617288	Hartman et al.	Nov 1971	A
3617335	Kumura et al.	Nov 1971	A
3619238	Kimura et al.	Nov 1971	A
3619239	Osada et al.	Nov 1971	A
3637337	Pilling	Jan 1972	A
3637581	Horioguchi et al.	Jan 1972	A
3642472	Mayo	Feb 1972	A
3647467	Grubb	Mar 1972	A
3652275	Baum et al.	Mar 1972	A
3660542	Adachi et al.	May 1972	A
3667954	Itano et al.	Jun 1972	A
3668188	King et al.	Jun 1972	A
3669925	King et al.	Jun 1972	A
3671096	Mackin	Jun 1972	A
3671251	Houle et al.	Jun 1972	A
3676690	McMillin et al.	Jul 1972	A
3678044	Adams	Jul 1972	A
3689565	Hoffmann et al.	Sep 1972	A
3694241	Guthrie et al.	Sep 1972	A
3695879	Laming et al.	Oct 1972	A
3697280	Strilko	Oct 1972	A
3705043	Zablak	Dec 1972	A
3707371	Files	Dec 1972	A
3729313	Smith	Apr 1973	A
3737628	Azure	Jun 1973	A
3765896	Fox	Oct 1973	A
3775130	Enomoto et al.	Nov 1973	A
3788849	Taguchi et al.	Jan 1974	A
3799773	Watarai et al.	Mar 1974	A
3800439	Sokolski et al.	Apr 1974	A
3801329	Sandner et al.	Apr 1974	A
3817752	Laridon et al.	Jun 1974	A
3840338	Zviak et al.	Oct 1974	A
3844790	Chang et al.	Oct 1974	A
RE28225	Heseltine et al.	Nov 1974	E
3870524	Watanabe et al.	Mar 1975	A
3873500	Kato et al.	Mar 1975	A
3879496	Lozano	Apr 1975	A
3887450	Gilano et al.	Jun 1975	A
3895949	Akamatsu	Jul 1975	A
3901779	Mani	Aug 1975	A
3910993	Avar et al.	Oct 1975	A
3914165	Gaske	Oct 1975	A
3914166	Rudolph et al.	Oct 1975	A
3915824	McGinniss	Oct 1975	A
3919323	Houlihan et al.	Nov 1975	A
3926641	Rosen	Dec 1975	A
3928264	Young, Jr. et al.	Dec 1975	A
3933682	Bean	Jan 1976	A
RE28789	Chang	Apr 1976	E
3952129	Matsukawa et al.	Apr 1976	A
3960685	Sano et al.	Jun 1976	A
3965157	Harrison	Jun 1976	A
3978132	Houlihan et al.	Aug 1976	A
3984248	Sturmer	Oct 1976	A
3988154	Sturmer	Oct 1976	A
4004998	Rosen	Jan 1977	A
4012256	Levinos	Mar 1977	A
4017652	Gruber	Apr 1977	A
4022674	Rosen	May 1977	A
4024324	Sparks	May 1977	A
4039332	Kokelenberg et al.	Aug 1977	A
4043819	Baumann	Aug 1977	A
4048034	Martan	Sep 1977	A
4054719	Cordes, III	Oct 1977	A
4056665	Tayler et al.	Nov 1977	A
4058400	Crivello	Nov 1977	A
4067892	Thorne et al.	Jan 1978	A
4071424	Dart et al.	Jan 1978	A
4073968	Miyamoto et al.	Feb 1978	A
4077769	Garcia	Mar 1978	A
4079183	Green	Mar 1978	A
4085062	Virgilio et al.	Apr 1978	A
4090877	Streeper	May 1978	A
4100047	McCarty	Jul 1978	A
4105572	Gorondy	Aug 1978	A
4107733	Schickedanz	Aug 1978	A
4110112	Roman et al.	Aug 1978	A
4111699	Krueger	Sep 1978	A
4114028	Baio et al.	Sep 1978	A
4126412	Masson et al.	Nov 1978	A
4141807	Via	Feb 1979	A
4144156	Kuesters et al.	Mar 1979	A
4148658	Kondoh et al.	Apr 1979	A
4162162	Dueber	Jul 1979	A
4171977	Hasegawa et al.	Oct 1979	A
4179577	Green	Dec 1979	A
4181807	Green	Jan 1980	A
4190671	Vanstone et al.	Feb 1980	A
4197080	Mee	Apr 1980	A
4199420	Photis	Apr 1980	A
4229172	Baumann et al.	Oct 1980	A
4232106	Iwasaki et al.	Nov 1980	A
4238492	Majoie	Dec 1980	A
4239843	Hara et al.	Dec 1980	A
4239850	Kita et al.	Dec 1980	A
4241155	Hara et al.	Dec 1980	A
4242430	Hara et al.	Dec 1980	A
4242431	Hara et al.	Dec 1980	A
4245018	Hara et al.	Jan 1981	A
4245995	Hugl et al.	Jan 1981	A
4246330	Hara et al.	Jan 1981	A
4248949	Hara et al.	Feb 1981	A
4250096	Kvita et al.	Feb 1981	A
4251622	Kimoto et al.	Feb 1981	A
4251662	Ozawa et al.	Feb 1981	A
4254195	Hara et al.	Mar 1981	A
4256493	Yokoyama et al.	Mar 1981	A
4256817	Hara et al.	Mar 1981	A
4258123	Nagashima et al.	Mar 1981	A
4258367	Mansukhani	Mar 1981	A
4259432	Kondoh et al.	Mar 1981	A
4262936	Miyamoto	Apr 1981	A
4268605	Hara et al.	May 1981	A
4268667	Anderson	May 1981	A
4269926	Hara et al.	May 1981	A
4270130	Houle et al.	May 1981	A
4271252	Hara et al.	Jun 1981	A
4271253	Hara et al.	Jun 1981	A
4272244	Schlick	Jun 1981	A
4276211	Singer et al.	Jun 1981	A
4277497	Fromantin	Jul 1981	A
4279653	Makihsima et al.	Jul 1981	A
4279982	Iwasaki et al.	Jul 1981	A
4279985	Nonogaki et al.	Jul 1981	A
4284485	Berner	Aug 1981	A
4288631	Ching	Sep 1981	A
4289844	Specht et al.	Sep 1981	A
4290870	Kondoh et al.	Sep 1981	A
4293458	Gruenberger et al.	Oct 1981	A
4298679	Shinozaki et al.	Nov 1981	A
4300123	McMillin et al.	Nov 1981	A
4301223	Nakamura et al.	Nov 1981	A
4302606	Barabas et al.	Nov 1981	A
4306014	Kunikane et al.	Dec 1981	A
4307182	Dalzell et al.	Dec 1981	A
4308400	Felder et al.	Dec 1981	A
4315807	Felder et al.	Feb 1982	A
4318705	Nowak et al.	Mar 1982	A
4318791	Felder et al.	Mar 1982	A
4321118	Felder et al.	Mar 1982	A
4335054	Blaser et al.	Jun 1982	A
4335055	Blaser et al.	Jun 1982	A
4336323	Winslow	Jun 1982	A
4343891	Aasen et al.	Aug 1982	A
4345011	Drexhage	Aug 1982	A
4347111	Gehlhaus et al.	Aug 1982	A
4349617	Kawashiri et al.	Sep 1982	A
4350753	Shelnut et al.	Sep 1982	A
4351893	Anderson	Sep 1982	A
4356255	Tachikawa et al.	Oct 1982	A
4357468	Szejtli et al.	Nov 1982	A
4359524	Masuda et al.	Nov 1982	A
4362806	Whitmore	Dec 1982	A
4367072	Vogtle et al.	Jan 1983	A
4367280	Kondo et al.	Jan 1983	A
4369283	Altschuler	Jan 1983	A
4370401	Winslow et al.	Jan 1983	A
4372582	Geisler	Feb 1983	A
4373017	Masukawa et al.	Feb 1983	A
4373020	Winslow	Feb 1983	A
4374984	Eichler et al.	Feb 1983	A
4376887	Greenaway et al.	Mar 1983	A
4383835	Preuss et al.	May 1983	A
4390616	Sato et al.	Jun 1983	A
4391867	Derick et al.	Jul 1983	A
4399209	Sanders et al.	Aug 1983	A
4400173	Beavan	Aug 1983	A
4401470	Bridger	Aug 1983	A
4416961	Drexhage	Nov 1983	A
4421559	Owatari	Dec 1983	A
4424325	Tsunoda et al.	Jan 1984	A
4425162	Sugiyama	Jan 1984	A
4425424	Altland et al.	Jan 1984	A
4426153	Libby et al.	Jan 1984	A
4434035	Eichler et al.	Feb 1984	A
4440827	Miyamoto et al.	Apr 1984	A
4447521	Tiers et al.	May 1984	A
4450227	Holmes et al.	May 1984	A
4460676	Fabel	Jul 1984	A
4467112	Matsuura et al.	Aug 1984	A
4475999	Via	Oct 1984	A
4477681	Gehlhaus et al.	Oct 1984	A
4489334	Owatari	Dec 1984	A
4495041	Goldstein	Jan 1985	A
4496447	Eichler et al.	Jan 1985	A
4500355	Shimada et al.	Feb 1985	A
4508570	Fugii et al.	Apr 1985	A
4510392	Litt et al.	Apr 1985	A
4523924	Lacroix	Jun 1985	A
4524122	Weber et al.	Jun 1985	A
4534838	Lin et al.	Aug 1985	A
4548896	Sabongi et al.	Oct 1985	A
4555474	Kawamura	Nov 1985	A
4557730	Bennett et al.	Dec 1985	A
4564560	Tani et al.	Jan 1986	A
4565769	Dueber et al.	Jan 1986	A
4567171	Mangum	Jan 1986	A
4571377	McGinniss et al.	Feb 1986	A
4595745	Nakano et al.	Jun 1986	A
4604344	Irving et al.	Aug 1986	A
4605442	Kawashita et al.	Aug 1986	A
4613334	Thomas et al.	Sep 1986	A
4614723	Schmidt et al.	Sep 1986	A
4617380	Hinson et al.	Oct 1986	A
4620875	Shimada et al.	Nov 1986	A
4620876	Fugii et al.	Nov 1986	A
4622286	Sheets	Nov 1986	A
4631085	Kawanishi et al.	Dec 1986	A
4632891	Banks et al.	Dec 1986	A
4632895	Patel et al.	Dec 1986	A
4634644	Irving et al.	Jan 1987	A
4638340	Iiyama et al.	Jan 1987	A
4647310	Shimada et al.	Mar 1987	A
4655783	Reinert et al.	Apr 1987	A
4663275	West et al.	May 1987	A
4663641	Iiyama et al.	May 1987	A
4668533	Miller	May 1987	A
4672041	Jain	Jun 1987	A
4698291	Koibuchi et al.	Oct 1987	A
4701402	Patel et al.	Oct 1987	A
4702996	Griffing et al.	Oct 1987	A
4704133	Reinert et al.	Nov 1987	A
4707161	Thomas et al.	Nov 1987	A
4707425	Sasagawa et al.	Nov 1987	A
4707430	Ozawa et al.	Nov 1987	A
4711668	Shimada et al.	Dec 1987	A
4713113	Shimada et al.	Dec 1987	A
4720450	Ellis	Jan 1988	A
4721531	Wildeman et al.	Jan 1988	A
4721734	Gehlhaus et al.	Jan 1988	A
4724021	Martin et al.	Feb 1988	A
4724201	Okazaki et al.	Feb 1988	A
4725527	Robillard	Feb 1988	A
4727824	Ducharme et al.	Mar 1988	A
4732615	Kawashita et al.	Mar 1988	A
4737190	Shimada et al.	Apr 1988	A
4737438	Ito et al.	Apr 1988	A
4740451	Kohara	Apr 1988	A
4745042	Sasago et al.	May 1988	A
4746735	Kruper, Jr. et al.	May 1988	A
4752341	Rock	Jun 1988	A
4755450	Sanders et al.	Jul 1988	A
4761181	Suzuki	Aug 1988	A
4766050	Jerry	Aug 1988	A
4766055	Kawabata et al.	Aug 1988	A
4770667	Evans et al.	Sep 1988	A
4771802	Tannenbaum	Sep 1988	A
4772291	Shibanai et al.	Sep 1988	A
4772541	Gottschalk	Sep 1988	A
4775386	Reinert et al.	Oct 1988	A
4786586	Lee et al.	Nov 1988	A
4789382	Neumann et al.	Dec 1988	A
4790565	Steed	Dec 1988	A
4800149	Gottschalk	Jan 1989	A
4803008	Ciolino et al.	Feb 1989	A
4808189	Oishi et al.	Feb 1989	A
4812139	Brodmann	Mar 1989	A
4812517	West	Mar 1989	A
4813970	Kirjanov et al.	Mar 1989	A
4822714	Sanders	Apr 1989	A
4831068	Reinert et al.	May 1989	A
4834771	Yamauchi et al.	May 1989	A
4837106	Ishikawa et al.	Jun 1989	A
4837331	Yamanishi et al.	Jun 1989	A
4838938	Tomida et al.	Jun 1989	A
4839269	Okazaki et al.	Jun 1989	A
4849320	Irving et al.	Jul 1989	A
4853037	Johnson et al.	Aug 1989	A
4853398	Carr et al.	Aug 1989	A
4854971	Gane et al.	Aug 1989	A
4857438	Loerzer et al.	Aug 1989	A
4861916	Kohler et al.	Aug 1989	A
4865942	Gottschalk et al.	Sep 1989	A
4874391	Reinert	Oct 1989	A
4874899	Hoelderich et al.	Oct 1989	A
4885395	Hoelderich	Dec 1989	A
4886774	Doi	Dec 1989	A
4892941	Dolphin et al.	Jan 1990	A
4895880	Gottschalk	Jan 1990	A
4900581	Stuke et al.	Feb 1990	A
4902299	Anton	Feb 1990	A
4902725	Moore	Feb 1990	A
4902787	Freeman	Feb 1990	A
4911732	Neumann et al.	Mar 1990	A
4911899	Hagiwara et al.	Mar 1990	A
4917956	Rohrbach	Apr 1990	A
4921317	Suzuki et al.	May 1990	A
4925770	Ichiura et al.	May 1990	A
4925777	Inoue et al.	May 1990	A
4926190	Lavar	May 1990	A
4933265	Inoue et al.	Jun 1990	A
4933948	Herkstroeter	Jun 1990	A
4937161	Kita et al.	Jun 1990	A
4940643	Sakai et al.	Jul 1990	A
4942113	Trundle	Jul 1990	A
4944988	Yasuda et al.	Jul 1990	A
4950304	Reinert et al.	Aug 1990	A
4952478	Miyagawa et al.	Aug 1990	A
4952680	Schmeidl	Aug 1990	A
4954380	Kanome et al.	Sep 1990	A
4954416	Wright et al.	Sep 1990	A
4956254	Washizu et al.	Sep 1990	A
4964871	Reinert et al.	Oct 1990	A
4965294	Ohngemach et al.	Oct 1990	A
4966607	Shinoki et al.	Oct 1990	A
4966833	Inoue	Oct 1990	A
4968596	Inoue et al.	Nov 1990	A
4968813	Rule et al.	Nov 1990	A
4985345	Hayakawa et al	Jan 1991	A
4987056	Imahashi et al.	Jan 1991	A
4988561	Wason	Jan 1991	A
4997745	Kawamura et al.	Mar 1991	A
5001330	Koch	Mar 1991	A
5002853	Aoai et al.	Mar 1991	A
5002993	West et al.	Mar 1991	A
5003142	Fuller	Mar 1991	A
5006758	Gellert et al.	Apr 1991	A
5013959	Kogelschatz	May 1991	A
5017195	Satou et al.	May 1991	A
5023129	Morganti et al.	Jun 1991	A
5025036	Carson et al.	Jun 1991	A
5026425	Hindagolla et al.	Jun 1991	A
5026427	Mitchell et al.	Jun 1991	A
5028262	Barlow, Jr. et al.	Jul 1991	A
5028792	Mullis	Jul 1991	A
5030243	Reinert	Jul 1991	A
5030248	Meszaros	Jul 1991	A
5034526	Bonham et al.	Jul 1991	A
5037726	Kojima et al.	Aug 1991	A
5045435	Adams et al.	Sep 1991	A
5045573	Kohler et al.	Sep 1991	A
5047556	Kohler et al.	Sep 1991	A
5049777	Mechtersheimer	Sep 1991	A
5053320	Robbillard	Oct 1991	A
5055579	Pawlowski et al.	Oct 1991	A
5057562	Reinert	Oct 1991	A
5068364	Takagaki et al.	Nov 1991	A
5069681	Bouwknegt et al.	Dec 1991	A
5070001	Stahlhofen	Dec 1991	A
5073448	Vieira et al.	Dec 1991	A
5074885	Reinert	Dec 1991	A
5076808	Hahn et al.	Dec 1991	A
5085416	Miyake et al.	Feb 1992	A
5085698	Ma et al.	Feb 1992	A
5087550	Blum et al.	Feb 1992	A
5089050	Vieira et al.	Feb 1992	A
5089374	Saeva	Feb 1992	A
5096456	Reinert et al.	Mar 1992	A
5096489	Laver	Mar 1992	A
5096781	Vieira et al.	Mar 1992	A
5098477	Vieira et al.	Mar 1992	A
5098793	Rohrbach et al.	Mar 1992	A
5098806	Robillard	Mar 1992	A
5106723	West et al.	Apr 1992	A
5108505	Moffat	Apr 1992	A
5108874	Griffing et al.	Apr 1992	A
5110706	Yumoto et al.	May 1992	A
5110709	Aoai et al.	May 1992	A
5114832	Zertani et al.	May 1992	A
5124723	Laver	Jun 1992	A
5130227	Wade et al.	Jul 1992	A
5133803	Moffatt	Jul 1992	A
5135940	Belander et al.	Aug 1992	A
5139572	Kawashima	Aug 1992	A
5139687	Borgher, Sr. et al.	Aug 1992	A
5141556	Matrick	Aug 1992	A
5141797	Wheeler	Aug 1992	A
5144964	Demian	Sep 1992	A
5147901	Rutsch et al.	Sep 1992	A
5153104	Rossman et al.	Oct 1992	A
5153105	Sher et al.	Oct 1992	A
5153166	Jain et al.	Oct 1992	A
5160346	Fuso et al.	Nov 1992	A
5160372	Matrick	Nov 1992	A
5166041	Murofushi et al.	Nov 1992	A
5169436	Matrick	Dec 1992	A
5169438	Matrick	Dec 1992	A
5173112	Matrick et al.	Dec 1992	A
5176984	Hipps, Sr. et al.	Jan 1993	A
5178420	Shelby	Jan 1993	A
5180425	Matrick et al.	Jan 1993	A
5180624	Kojima et al.	Jan 1993	A
5180652	Yamaguchi et al.	Jan 1993	A
5181935	Reinert et al.	Jan 1993	A
5185236	Shiba et al.	Feb 1993	A
5187045	Bonham et al.	Feb 1993	A
5187049	Sher et al.	Feb 1993	A
5190565	Berenbaum et al.	Mar 1993	A
5190710	Kletecka	Mar 1993	A
5190845	Hashimoto et al.	Mar 1993	A
5193854	Borowski, Jr. et al.	Mar 1993	A
5196295	Davis	Mar 1993	A
5197991	Rembold	Mar 1993	A
5198330	Martic et al.	Mar 1993	A
5202209	Winnik et al.	Apr 1993	A
5202210	Matsuoka et al.	Apr 1993	A
5202211	Vercoulen	Apr 1993	A
5202212	Shin et al.	Apr 1993	A
5202213	Nakahara et al.	Apr 1993	A
5202215	Kanakura et al.	Apr 1993	A
5202221	Imai et al.	Apr 1993	A
5205861	Matrick	Apr 1993	A
5208136	Zanoni et al.	May 1993	A
5209814	Felten et al.	May 1993	A
5219703	Bugner et al.	Jun 1993	A
5221334	Ma et al.	Jun 1993	A
5224197	Zanoni et al.	Jun 1993	A
5224476	Schultz et al.	Jul 1993	A
5224987	Matrick	Jul 1993	A
5226957	Wickramanayake et al.	Jul 1993	A
5227022	Leonhardt et al.	Jul 1993	A
5241059	Yoshinaga	Aug 1993	A
5244476	Schulz et al.	Sep 1993	A
5250109	Chan et al.	Oct 1993	A
5254429	Gracia et al.	Oct 1993	A
5256193	Winnik et al.	Oct 1993	A
5258274	Helland et al.	Nov 1993	A
5261953	Vieira et al.	Nov 1993	A
5262276	Kawamura	Nov 1993	A
5268027	Chan et al.	Dec 1993	A
5270078	Walker et al.	Dec 1993	A
5271764	Winnik et al.	Dec 1993	A
5271765	Ma	Dec 1993	A
5272201	Ma et al.	Dec 1993	A
5275646	Marshall et al.	Jan 1994	A
5279652	Kaufmann et al.	Jan 1994	A
5282894	Albert et al.	Feb 1994	A
5284734	Blum et al.	Feb 1994	A
5286286	Winnik et al.	Feb 1994	A
5286288	Tobias et al.	Feb 1994	A
5294528	Furutachi	Mar 1994	A
5296275	Goman et al.	Mar 1994	A
5296556	Frihart	Mar 1994	A
5298030	Burdeska et al.	Mar 1994	A
5300403	Angelopolus et al.	Apr 1994	A
5300654	Nakajima et al.	Apr 1994	A
5302195	Helbrecht	Apr 1994	A
5302197	Wickramanayke et al.	Apr 1994	A
5310778	Shor et al.	May 1994	A
5312713	Yokoyama et al.	May 1994	A
5312721	Gesign	May 1994	A
5324349	Sano et al.	Jun 1994	A
5328504	Ohnishi	Jul 1994	A
5330860	Grot et al.	Jul 1994	A
5334455	Noren et al.	Aug 1994	A
5338319	Kaschig et al.	Aug 1994	A
5340631	Matsuzawa et al.	Aug 1994	A
5340854	Martic et al.	Aug 1994	A
5344483	Hinton	Sep 1994	A
5356464	Hickman et al.	Oct 1994	A
5362592	Murofushi et al.	Nov 1994	A
5368689	Agnemo	Nov 1994	A
5372387	Wajda	Dec 1994	A
5372917	Tsuchida et al.	Dec 1994	A
5374335	Lindgren et al.	Dec 1994	A
5376503	Audett et al.	Dec 1994	A
5383961	Bauer et al.	Jan 1995	A
5384186	Trinh	Jan 1995	A
5393580	Ma et al.	Feb 1995	A
5401303	Stoffel et al.	Mar 1995	A
5401562	Akao	Mar 1995	A
5415686	Kurabayashi et al.	May 1995	A
5415976	Ali	May 1995	A
5424407	Tanaka et al.	Jun 1995	A
5425978	Berneth et al.	Jun 1995	A
5426164	Babb et al.	Jun 1995	A
5427415	Chang	Jun 1995	A
5429628	Trinh et al.	Jul 1995	A
5431720	Nagai et al.	Jul 1995	A
5432274	Luong et al.	Jul 1995	A
5445651	Thoen et al.	Aug 1995	A
5445842	Tanaka et al.	Aug 1995	A
5455074	Nohr et al.	Oct 1995	A
5455143	Ali	Oct 1995	A
5459014	Nishijima et al.	Oct 1995	A
5464472	Horn et al.	Nov 1995	A
5466283	Kondo et al.	Nov 1995	A
5474691	Severns	Dec 1995	A
5475080	Gruber et al.	Dec 1995	A
5476540	Shields et al.	Dec 1995	A
5479949	Battard et al.	Jan 1996	A
5489503	Toan	Feb 1996	A
5498345	Jollenbeck et al.	Mar 1996	A
5501774	Burke	Mar 1996	A
5503664	Sano et al.	Apr 1996	A
5509957	Toan et al.	Apr 1996	A
5531821	Wu	Jul 1996	A
5532112	Kohler et al.	Jul 1996	A
5541633	Winnik et al.	Jul 1996	A
5543459	Hartmann et al.	Aug 1996	A
5569529	Becker et al.	Oct 1996	A
5571313	Mafune et al.	Nov 1996	A
5575891	Trokhan et al.	Nov 1996	A
5580369	Belding et al.	Dec 1996	A
5591489	Dragner et al.	Jan 1997	A
5607803	Murofushi et al.	Mar 1997	A
5616443	Nohr et al.	Apr 1997	A
5635297	Ogawa et al.	Jun 1997	A
5643356	Nohr et al.	Jul 1997	A
5643631	Donigian et al.	Jul 1997	A
5645964	Nohr et al.	Jul 1997	A
5672392	De Clercq et al.	Sep 1997	A
5681380	Nohr et al.	Oct 1997	A
5683843	Nohr et al.	Nov 1997	A
5685754	Nohr et al.	Nov 1997	A
5686503	Nohr et al.	Nov 1997	A
5700582	Sargeant et al.	Dec 1997	A
5700850	Nohr et al.	Dec 1997	A
5705247	Arai et al.	Jan 1998	A
5709955	Nohr et al.	Jan 1998	A
5709976	Malhotra	Jan 1998	A
5721287	Nohr et al.	Feb 1998	A
5733693	Nohr et al.	Mar 1998	A
5739175	Nohr et al.	Apr 1998	A
5747550	Nohr et al.	May 1998	A
5773182	Nohr et al.	Jun 1998	A
5782963	Nohr et al.	Jul 1998	A
5786132	Nohr et al.	Jul 1998	A
5798015	Nohr et al.	Aug 1998	A
5811199	MacDonald et al.	Sep 1998	A
5837429	Nohr et al.	Nov 1998	A
5849411	Nohr et al.	Dec 1998	A
5855655	Nohr et al.	Jan 1999	A
5865471	Nohr et al.	Feb 1999	A

Foreign Referenced Citations (212)

Number	Date	Country
103085	Apr 1937	AU
1262488	Sep 1988	AU
620075	May 1962	BE
637169	Mar 1964	BE
413257	Oct 1932	CA
458808	Dec 1936	CA
460268	Oct 1949	CA
461082	Nov 1949	CA
463021	Feb 1950	CA
463022	Feb 1950	CA
465495	May 1950	CA
465496	May 1950	CA
465499	May 1950	CA
483214	May 1952	CA
517364	Oct 1955	CA
537687	Mar 1957	CA
552565	Feb 1958	CA
571792	Mar 1959	CA
779239	Feb 1968	CA
930103	Jul 1973	CA
2053094	Apr 1992	CA
603767	Aug 1978	CH
197808	May 1988	CH
94118	May 1958	CZ
1047787	Dec 1957	DE
1022801	Jan 1958	DE
1039835	Sep 1958	DE
1040562	Oct 1958	DE
1045414	Dec 1958	DE
1047013	Dec 1958	DE
1132450	Jul 1962	DE
1132540	Jul 1962	DE
1154069	Sep 1963	DE
1240811	May 1967	DE
2202497	Aug 1972	DE
2432563	Feb 1975	DE
2437380	Feb 1975	DE
2444520	Mar 1975	DE
2416259	Oct 1975	DE
2714978	Oct 1977	DE
2722264	Nov 1978	DE
158237	Jan 1983	DE
3126433	Jan 1983	DE
3415033	Oct 1984	DE
271512	Sep 1989	DE
3921600	Jan 1990	DE
3833437	Apr 1990	DE
3833438	Apr 1990	DE
004036328	Jul 1991	DE
4132288	Apr 1992	DE
4126461	Feb 1993	DE
0003884	Sep 1979	EP
0029284	May 1981	EP
0127574	Dec 1984	EP
0223587	May 1987	EP
0262533	Apr 1988	EP
0280458	Aug 1988	EP
0308274	Mar 1989	EP
0371304	Jun 1990	EP
0373662	Jun 1990	EP
0375160	Jun 1990	EP
0351615	Oct 1990	EP
0390439	Oct 1990	EP
0458140	Oct 1991	EP
0458140	Nov 1991	EP
0468465	Jan 1992	EP
0542286	May 1993	EP
000571190	Nov 1993	EP
0608433	Aug 1994	EP
0609159	Aug 1994	EP
0639664	Feb 1995	EP
0 716 929	Jun 1996	EP
0755984	Jan 1997	EP
2245010	Apr 1975	FR
2383157	Oct 1978	FR
275245	Oct 1928	GB
349339	May 1931	GB
355686	Aug 1931	GB
399753	Oct 1933	GB
441085	Jan 1936	GB
463515	Apr 1937	GB
492711	Sep 1938	GB
518612	Mar 1940	GB
539912	Sep 1941	GB
626727	Jul 1947	GB
600451	Apr 1948	GB
616362	Jan 1949	GB
618616	Feb 1949	GB
779389	Jul 1957	GB
1372884	Nov 1974	GB
2143657	Apr 1985	GB
662500	Apr 1964	IT
4315663	Jul 1968	JP
4726653	Jul 1972	JP
4745409	Nov 1972	JP
49-8909	Feb 1974	JP
5065592	Jun 1975	JP
51-17802	Feb 1976	JP
53-104321	Sep 1978	JP
55-62059	May 1980	JP
55-90506	Jul 1980	JP
56-8134	Jan 1981	JP
0014233	Feb 1981	JP
5614569	Feb 1981	JP
56-24472	Mar 1981	JP
56-36556	Apr 1981	JP
5761055	Apr 1982	JP
57128283	Aug 1982	JP
57171775	Oct 1982	JP
58-124452	Jul 1983	JP
58-125770	Jul 1983	JP
58-222164	Dec 1983	JP
5989360	May 1984	JP
29219270	Dec 1984	JP
59-219270	Apr 1985	JP
60-192729	Oct 1985	JP
60239739	Nov 1985	JP
60239740	Nov 1985	JP
60239741	Nov 1985	JP
60239743	Nov 1985	JP
61-288	Jan 1986	JP
613781	Jan 1986	JP
61-14994	Jan 1986	JP
61-14995	Jan 1986	JP
61-21184	Jan 1986	JP
61-25885	Feb 1986	JP
61-30592	Feb 1986	JP
61-40366	Feb 1986	JP
61-77846	Apr 1986	JP
61-128973	Jun 1986	JP
61-97025	Sep 1986	JP
61-222789	Oct 1986	JP
61-247703	Nov 1986	JP
61-285403	Dec 1986	JP
627703	Jan 1987	JP
62-97881	May 1987	JP
62-100557	May 1987	JP
62127281	Jun 1987	JP
63-43959	Feb 1988	JP
63-48370	Mar 1988	JP
6395439	Apr 1988	JP
6395440	Apr 1988	JP
6395445	Apr 1988	JP
6395446	Apr 1988	JP
6395447	Apr 1988	JP
6395448	Apr 1988	JP
6395449	Apr 1988	JP
6395450	Apr 1988	JP
63151946	Jun 1988	JP
63-164953	Jul 1988	JP
63-165498	Jul 1988	JP
63-223077	Sep 1988	JP
63-223078	Sep 1988	JP
63-243101	Oct 1988	JP
63-199781	Dec 1988	JP
64-15049	Jan 1989	JP
6429337	Jan 1989	JP
64-40948	Feb 1989	JP
89014948	Mar 1989	JP
1-128063	May 1989	JP
1146974	Jun 1989	JP
01210477	Aug 1989	JP
1288854	Nov 1989	JP
2-58573	Feb 1990	JP
561220	Mar 1990	JP
292957	Apr 1990	JP
2179642	Jul 1990	JP
2282261	Nov 1990	JP
3-134072	Jun 1991	JP
03163566	Jul 1991	JP
3-170415	Jul 1991	JP
3-206439	Sep 1991	JP
3-258867	Nov 1991	JP
5134447	Nov 1991	JP
3-203694	Dec 1991	JP
3284668	Dec 1991	JP
4023884	Jan 1992	JP
4023885	Jan 1992	JP
4-45174	Feb 1992	JP
4100801	Apr 1992	JP
4-136075	May 1992	JP
0435687	Dec 1992	JP
543806	Feb 1993	JP
5080506	Apr 1993	JP
05119506	May 1993	JP
5-140498	Jun 1993	JP
2-219869	Sep 1993	JP
5263067	Oct 1993	JP
680915	Mar 1994	JP
6116555	Apr 1994	JP
6116556	Apr 1994	JP
6116557	Apr 1994	JP
6-175584	Jun 1994	JP
6214339	Aug 1994	JP
6256494	Sep 1994	JP
6256633	Sep 1994	JP
424756	Sep 1998	JP
7113828	Apr 1972	NL
1310767	May 1987	RU
1772118	Oct 1992	SU
9211295	Jul 1992	WO
9306597	Apr 1993	WO
9401503	Jan 1994	WO
9422500	Oct 1994	WO
9422501	Oct 1994	WO
9504955	Feb 1995	WO
9528285	Oct 1995	WO
9600740	Jan 1996	WO
9619052	Jun 1996	WO
9322335	Jul 1996	WO
9624636	Aug 1996	WO
9720000	Jun 1997	WO

Non-Patent Literature Citations (224)

Entry
Kubat et al. “Photophysical properties of metal complexes of meso-tetrakis (40sulphonatophenyl) porphyrin,” J. Photochem. and Photobiol. 96 pp 93-97 (1996).
Abstract for WO 95/00343—A1 Textiles: Paper: Cellulose p. 7 (1995).
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).
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).
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).
Abstract Of Patent, JP 405125318 ( Mitsubishi Kasei Corp.), May 21, 1993. (Abstract).
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 pp 80-87 (1993).
Hamilton, D.P. “Tired of Shredding? New Ricoh Method Tries Different Tack” Wall Street Journal B2 (1993).
“Cyclodextrins: A Breakthrough for Molecular Encapsulation” American Maize Products Co. (AMAIZO) (1993).
Duxbury “The Photochemistry and Photophysics of Triphenylmethane Dyes in Solid Liquid Media” Chemical Review 93 pp 381-433 (1993).
Abstract of patent, JP 04-351603 (Dec. 7, 1992).
Abstract of patent, JP 04-351602 (1992).
Derwent Publications Ltd., London, JP 404314769 (Citizen Watch Co. Ltd.), Nov. 5, 1992. (Abstract).
Abstract of patent, JP 04315739 (1992).
Derwent Publications Ltd., London, JP 04300395 (Funai Denki KK), Nov. 23, 1992. (Abstract).
Derwent Publications Ltd., London, JP 404213374 (Mitsubishi Kasei Corp), Aug. 4, 1992. (Abstract).
Abstract of patent, JP 04-210228 (1992).
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).
Abstract of patent, JP 04-81401 (1992).
Kogelschatz “Silent-discharge driven excimer UV sources and their applications” Applied Surface Science pp 410-423 (1992).
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).
Patent Abstracts of Japan, JP 03184896 (Dainippon Printing Co Ltd.) Aug. 12, 1991.
Derwent Publications Ltd., London, JP 3167270 (Mitsubishi Kasei Corp), Jul. 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).
Kogelschatz, U. et al. “New Excimer UV Sources for Industrial Applications” ABB Review 391 pp 1-10 (1991).
Abstract of patent, JP 03-41165 (1991).
“Coloring/Decoloring Agent for Tonor Used Developed” Japan Chemical Week (1991).
Braithwaite, M., et al. “Formulation” Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints IV pp 11-12 (1991).
Scientific Polymer Products, Inc. Brochure 24-31 (1991).
Dietliker, K. “Photoiniators for Free Radical and Cationinc Polymerisation” Chem & Tech of UV & EB Formulation for Coatings, Inks & Paints III pp 61, 63, 229-232, 280, 405, (1991).
Esrom et al. “Large area Photochemical Dry Etching of Polymers iwth Incoherent Excimer UV Radiation” MRS Materials Research Society pp 1-7 (1991).
Esrom et al. Excimer Laser-Induced Decompostion of Aluminum Nitride Materials Research Society Fall Meeting pp 1-6 (1991).
Esrom et al. “Metal deposition with a windowless VUV excimer source” Applied Surface Science pp 1-5 (1991).
Esrom “Excimer Laser-Induced Surface Activation of Aln for Electroless Metal Deposition” Mat. Res. Sco.lSymp. Proc. 204 pp 457-465 (1991).
Zhang et al. “UV-induced decompositin of adsorbed Cu-acetylacetonate films at room temperature for electroless metal plating” Applied Surface Science pp 1-6 (1991).
“German company develops reusable paper” Pulp & Paper (1991).
Abstract of patent, JP 02289652 (1990).
Ohashi et al. “Molecular Mechanics Studies on Inclusion Compounds of Cyanine Dye Monomers and Dimers in Cyclodextrin Cavities,” J. Am. Chem. Soc. 112 pp 5824-5830 (1990).
Kogelschatz et al. “New Incoherent Ultraviolet Excimer Sources for Photolytic Material Deposition,” Laser Und Optoelektronik (1990).
Patent Abstracts of Japan, JP 02141287 (Dainippon Printing Co Ltd.) May 30, 1990.
Abstract of Patent, JP 0297957, (Fuji Xerox Co., Ltd.) (1990).
Derwent Publications Ltd., London, JP 2091166 (Canon KK), Mar. 30, 1990. (Abstract).
Esrom et al. “Metal Deposition with Incoherent Excimer Radiation” Mat. Res. Soc. Symp. Proc. 158 pp 189-198 (1990).
Esrom “UV Excimer Laer-Induced Deposition of Palladium from palladiym Acetate Films” Mat. Res. Soc. Symp. Proc. 158 pp 109-117 (1990).
Kogelschatz, U. “Silent Discharges for the Generation of ultraviolet and vacuum ultraviolet excimer radiation” Pure & Applied Chem. 62 pp 1667-74 (1990).
Esrom et al. “Investigation of the mechanism of the UV-induced palladium depostions processf from thin solid palladium acetate films” Applied Surface Science 46 pp 158-162 (1990).
Zhang et al. “VUV synchrotron radiation processing of thin palladium acetate spin-on films for metallic surface patterning” Applied Surface Science 46 pp 153-157 (1990).
Brennan et al. “Tereoelectronic effects in ring closure reactions: the 2′-hydroxychalcone—flavanone equilibrium, and related systems,” Canadian J. Chem. 68 (10) pp. 1780-1785 (1990).
Abstract of patent, JP 01-299083 (1989).
Derwent Publications Ltd., London, J,0, 1182379 (Canon KK), Jul. 20, 1989. (Abstract).
Derwent Publications Ltd., London, JO 1011171 (Mitsubishi Chem Ind. KK.), Jan. 13, 1989 (Absract).
Gruber, R.J., et al. “Xerographic Materials” Encyclopedia of Polymer Science and Engineering 17 pp 918-943 1989.
Pappas, S.P. “Photocrosslinking” Comph. Pol. Sci. 6 pp 135-148 1989.
Pappas, S.P. “Photoinitiated Polymerization” Comph. Pol. Sci. 4 pp 337-355 1989.
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 3b] 1989.
Esrom et al. “UV excimer laser-induced pre-nucleation of surfaces followed by electroless metallization” Chemtronics 4 pp 216-223 1989.
Esrom et al. “VUV light-induced depostion of palladium using an incoherent Xe2* excimer source” Chemtronics 4 1989.
Esrom et al. “UV Light-Induced Depostion of Copper Films” C5-719—C5-725 1989.
Falbe et al. Rompp Chemie Lexikon 9 170 1989.
Allen, Norman S. Photopolymerisation and Photoimaging Science and Technology pp. 188-199; 210-239 (1989).
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).
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 B14Sr3Ca3Cu4O16+× superconducting thin films from citrate precursors,” Appl. Phys. Lett. 52 (2 2180-2182 (1988).
Abstract of patent, JP 63-144329 (1988).
Abstract of patent, JP 63-130164 (1988).
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,J6 3108073 (Konishiroku Photo KK), May 12, 1988 (Abstract).
Abstract of patent, JP 61-77846 (1988).
Abstract of patent, JP 63-73241 (1988).
Abstract of patent, JP 6347762, (1988).
Abstract of patent, JP 63-47763, (1988).
Abstract of patent, JP 63-47764, (1988).
Abstract of patent, JP 63-47765, (1988).
Eliasson, B., et al. “UV Excimer Radiation from Dielectric-Barrier Discharges” Applied Physics B 46 pp 299-303 (1988).
Eliasson et al. “New Trends in High Intensity UV Generation” EPA Newsletter (32) pp 29-40 (1988).
Cotton, F.A. “Oxygen: Group Via(16)” Advanced Inorganic Chemistry 5th ed. pp 473-474 (1988).
Derwent Publications, Ltd., London, J6 2270665 (Konishiroku Photo KK), Nov. 25, 1987 (Abstract).
Abstract of patent, JP 62-215261 (1987).
Database WPI, Derwent Publications Ltd., London, JP 62032082 (Mitsubishi Denki KK), Feb. 12, 1987. (Abstract).
Abstract of patent, JP 62-32082 (1987).
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) pp 1628-1632 (1987).
Al-Ismail et al. “Some experimental results on thin polypropylene films loaded with finely-dispersed copper” Journal of Materials Science pp 415-418 (1987).
Baufay et al. “Optical self-regulation during laser-induced oxidation of copper” J. Appl. Phys 61 (9) pp 4640-4651 (1987).
Derwent Publications Ltd., London, JA 0284478 (Sanyo Chem Ind Ltd.), Dec. 15, 1986 (Abstract).
Abstract of patent, JP 61251842 (1986).
Database WPI, Derwent Publications Ltd., London, GB; Su, A, 1098210 (Kutulya L A) Jun. 23, 1986.
Abstract of patent, JP 61-97025 (1986).
Abstract of patent, JP 61-87760 (1986).
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 (sumitomo 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).
Jellinek, H.H.G. et al. “Evolution of H2O and CO2 During the Copper-Catalyzed Oxidation of Isotactic Polypropylene,” J. Polymer Sci. 24 pp 389-403 (1986).
Jellinek, 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 pp 503-510 (1986).
John J. Eisch and Ramiro Sanchez “Selective, Oxophilic Imination of Ketones with Bis (dichloroaluminum) Phenylimide” J. Org. Chem. 51 (10) pp 1848-1852 (1986).
Derwent Publications Ltd., London, J6 0226575 (Sumitomo Chem Ind Ltd.), Oct. 11, 1985 (Abstract).
Abstract of patent, JP 60-156761 (1985).
Derwent Publications Ltd., London, J,A, 0011451 (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).
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 Inclusions Complexes” Inclusion Compounds—Structural Aspects of Inclusion Compounds formed by Organic Host 2 pp 231-259 (1984).
Szejtli “Industrial Applications of Cyclodextrins” Inclusion Compounds: Physical Prop. & Applns 3 pp 331-390 (1984).
Kano et al. “Three-Component Complexes of Cyclodextrins. Exciplex Formation in Cyclodextrin Cavity,” J. Inclusion Phenomena 2 pp. 737-746 (1984).
Suzuki et al. “Spectroscopic Investigation of Cyclodextrin Monomers, Derivatives, Polymers and Azo Dyes,” J. Inclusion Phenomena 2 pp. 715-724 (1984).
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 pp 176-181 (1983).
Connors, K.A. “Application of a stoichiometric model of cyclodextrin complex formation” Chemical Abstracts 98 598 [No. 98:53067g] (1983).
Abstract Of Patent, EP 0065617 (IBM Corp.), Dec. 1, 1982 (Abstract).
Derwent Publications Ltd., London, J,A, 0187289 (Honshu Paper Mfg KK), Nov. 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).
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).
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 pp 241-274 (1981).
Komiyama et al. “0ne-Pot Preparation of 4-Hydroxychalcone β-Cyclodextrin as Catalyst,” Makromol. Chem. 2 pp 733-734 (1981).
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) pp 564-567 (1980).
Semple et al. “Synthesis of Functionalized Tetrahydrofurans,” Tetrahedron Letters 81 pp. 4561-4564 (1980).
Kirk-Othmer “Film Deposition Techniques,” Encyclopedia of Chemical Technology 10 pp 247-283 (1980).
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 pp 85-87 (1979).
“Color imaging devices and color filter arrays using photo-bleachable dyes” Research Disclosure pp 22-23 (1979).
Wolff, N.E., et al. “Electrophotography” Kirk-Othmer Encyclopedia of Chemical Technology 8 pp. 794-826 (1979).
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).
Lamberts, R.L. “Recording color grid patterns with lenticules” Research Disclosure 18-19 [No. 12923] (1975).
Karmanova, L.S. et al. “Light stabilizers of daytime fluorescent paints” Chemical Abstracts 82 147 [No. 59971p] (1975).
Prokopovich, B. et al. “Selection of effective photoinducers for rapid hardening of polyester varnish PE-250” Chemical Abstracts 83 131 [No. 81334a] (1975).
“Variable Contrast Printing System” Research Disclosure 19 [No. 12931] (1975).
Lakshman “Electronic Absorption Spectrum of Copper Formate Tetrahydrate” Chemical Physics Letters 31 (2) pp 331-334 (1975).
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) pp 1520-1521 (1974).
“Darocur 1173: Liquid Photoiniator for Ultraviolet Curing of Coatings” (1974).
Hosokawa et al. “Ascofuranone, an antibiotic from Ascochyta,” Japan Kokai 73 91,278 (Nov. 28, 1973) MERCK Incex 80 p. 283; abstract 94259t.
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).
Derwent Publications, Ltd., London SU 292698-S Jan. 15, 1971 (abstract) (1971).
Derwent World Patents Index,CS 120380 (Korcourek, Jan) Oct. 15, 1966.
Ridgon, J.E. “In Search of Paper that Spies Can't Copy” Wall Street Journal (No date).
Chatterjee,S. et al. “Photochemistry of Carbocyanine Alkyltriphenylborte Salts: Intra-Ion-Pair Electron Transfer and the Chemistry of Boranyl Radicals” J. Am. Chem. Soc. 112 6329-6338 (No date).
“Assay—Physical and Chemical Analysis of Complexes” AMAIZO (No date).
“Cyclodextrin” AMAIZO (No date).
“Beta Cyclodextrin Polymer (BCDP)” AMAIZO (No date).
“Chemically Modified Cyclodextrins” AMAIZO (No date).
“Cyclodextrin Complexation” American Maize Products Co. (No date).
“Monomers” Scientific Polymer Products Inc. (No date).
Suppan, Paul “Quenching of Excited States” Chemistry and Light pp 65-69 (No date).
Yamaguchi, H. et al. “Supersensitization. Aromatic ketones as supersensitizers” Chemical Abstracts 53 107 (d) (No date).
Stecher, H. “Ultraviolet-absorptive additives in adhesives, lacquers and plastics” Chemical Abstracts 53 14579 (c) (No date).
Maslennikov, A.S. “Coupling of diazonium salts with ketones” Chemical Abstracts 60 3128e (No date).
Derwent Publications Ltd., London, 4 9128022 (No date).
Abstract of Patent, JP 405195450 (No date).
Rose, Philip I. “Gelatin,” Encyclopedia of Chemical Technology 7 pp 488-513 (No date).

Provisional Applications (1)

	Number	Date	Country
	60/000570	Jun 1995	US

Continuations (1)

	Number	Date	Country
Parent	PCT/US96/04689	Apr 1996	US
Child	08/983159		US

Continuation in Parts (8)

	Number	Date	Country
Parent	08/461372	Jun 1995	US
Child	PCT/US96/04689		US
Parent	08/403240	Mar 1995	US
Child	08/461372		US
Parent	08/373958	Jan 1995	US
Child	08/403240		US
Parent	08/360501	Dec 1994	US
Child	08/373958		US
Parent	08/359670	Dec 1994	US
Child	08/360501		US
Parent	08/258858	Jun 1994	US
Child	08/359670		US
Parent	08/183683	Jan 1994	US
Child	08/258858		US
Parent	08/119912	Sep 1993	US
Child	08/183683		US

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

Abstract

Description

Claims

CROSS-REFERENCE TO RELATED APPLICATION

US Referenced Citations (666)

Foreign Referenced Citations (212)

Non-Patent Literature Citations (224)

Provisional Applications (1)

Continuations (1)

Continuation in Parts (8)