Claims
- 1. A water soluble, ester-terminated, poly(alkyleneoxy)-substituted methine colorant of the formula: ##STR34## wherein: AR is an unsubstituted or substituted aromatic or hetero-aromatic group; X is selected from nitrogen or oxygen; R is unsubstituted or substituted straight or branched alkylene of 2-4 carbons or mixtures thereof; R.sub.1 is selected from or an unsubstituted or substituted alkyl, cycloalkyl or phenyl moiety containing one to about 10 carbons, or a group of the formula: ##STR35## wherein R.sub.3 is or alkyl of one to about ten carbons, and d is zero when X is oxygen and one when X is nitrogen; R.sub.2 is hydrogen or alkyl of one to about five carbons; a and b are each an integer independently selected from one to about forty wherein a+b is an integer of from about 6 to about 80, and z is a divalent vinylic carbon atom which is covalently bonded to a group or moiety selected from cyano, vinyl carbon, sulfide, sulfoxide, sulfone, allylic oxygen, thiocyano, or carbonyl which is not part of an amide, carboxylic acid or carboxylic acid salt moiety.
- 2. A methine colorant of claim 1 wherein X is nitrogen.
- 3. A methine colorant of claim 1 wherein X is oxygen.
- 4. A methine colorant as defined in claim 1 having the formula: ##STR36## wherein: R.sub.5 and R.sub.6 are each selected from hydrogen, alkyl, alkoxy, halogen or trifluoromethyl; R.sub.8 is selected from cyano, alkylsulfonyl, cycloalkylsulfonyl, arylsulfonyl, or lower carbalkoxy containing one to about ten carbons, acetyl or benzoyl; and R.sub.7 is selected from alkyl, cycloalkyl or unsubstituted or substituted phenyl.
- 5. A methine colorant as defined in claim 1 having the formula: ##STR37## wherein: R.sub.5 and R.sub.6 are each selected from hydrogen, alkyl, alkoxy, halogen or trifluoromethyl; R.sub.8 is selected from cyano, alkylsulfonyl, cycloalkylsulfonyl, arylsulfonyl, or lower carbalkoxy containing one to about ten carbons, acetyl or benzoyl; and R.sub.7 is selected from alkyl, cycloalkyl or unsubstituted or substituted phenyl.
- 6. A methine colorant as defined in claim 1 having the formula: ##STR38## wherein: R.sub.5 is selected from alkyl, alkoxy, halogen or trifluoromethyl; R.sub.7 is selected from alkyl, cycloalkyl or unsubstituted or substituted phenyl; R.sub.8 is selected from cyano, alkylsulfonyl, cycloalkylsulfonyl, arylsulfonyl, or lower carbalkoxy containing from one to about ten carbons, acetyl or benzoyl; and R.sub.11, R.sub.13 and R.sub.14 are each selected from or lower alkyl.
- 7. A methine colorant as defined in claim 1 having the formula: ##STR39## wherein: R.sub.5 and R.sub.6 are each selected from H, alkyl, alkoxy, halogen or trifluoromethyl; and R.sub.15 is selected from H, lower alkyl, phenyl or phenyl substituted with lower alkyl, lower alkoxy or halogen.
- 8. A methine colorant as defined in claim 1 having the formula: ##STR40## wherein; R.sub.5 and R.sub.6 are each selected from H, alkyl, alkoxy, halogen or trifluoromethyl; and R.sub.15 is selected from H, lower alkyl, phenyl or phenyl substituted with lower alkyl lower alkoxy or halogen. ##STR41##
- 9. A methine colorant as defined in claim 1 having the formula:
- wherein: R.sub.11, R.sub.13 and R.sub.14 are each selected from or lower alkyl; and R.sub.15 is selected from H, lower alkyl, phenyl or phenyl substituted with lower alkyl, lower alkoxy or halogen.
- 10. A methine colorant as defined in claim 1 having the formula: ##STR42## wherein: R.sub.5 and R.sub.6 are each selected from H, alkyl, alkoxy, halogen, or trifluoromethyl; and R.sub.16 and R.sub.17 are each selected from oxygen or CR.sub.8 R.sub.8 wherein each R.sub.8 is selected from cyano, alkylsulfonyl, cycloalkylsulfonyl, arylsulfonyl, or lower carbalkoxy containing from one to about ten carbons, acetyl or benzoyl.
- 11. A methine colorant as defined in claim 1 having the formula: ##STR43## wherein: e is zero, one or two; each R.sub.5 and R.sub.6 is selected from H, alkyl, alkoxy, halogen, or trifluoromethyl; and R.sub.16 is selected from oxygen or CR.sub.8 R.sub.8 wherein each R.sub.8 is selected from cyano, alkylsulfonyl, cycloalkylsulfonyl, arylsulfonyl, or lower carbalkoxy containing from one to about ten carbons, acetyl or benzoyl.
- 12. A methine colorant as defined in claim 1 having the formula: ##STR44## wherein: R.sub.5 and R.sub.6 are each selected from H, alkyl, alkoxy, halogen, or trifluoromethyl; R.sub.11, R.sub.13 and R.sub.14 are each selected from or lower alkyl; e is 0, 1 or 2; and R.sub.16 is selected from oxygen or CR.sub.8 R.sub.8 wherein each R.sub.8 is selected from cyano, alkylsulfonyl, cycloalkylsulfonyl, arylsulfonyl, or lower carbalkoxy containing from one to about ten carbons, acetyl or benzoyl.
- 13. A methine colorant as defined in claim 1 having the formula: ##STR45## wherein: each R.sub.5 and R.sub.6 is selected from H, alkyl, alkoxy, halogen, or trifluoromethyl; e is 1, 2 or 3; and R.sub.16 is selected from oxygen or CR.sub.8 R.sub.8 wherein each R.sub.8 is selected from cyano, alkylsulfonyl, cycloalkyl-sulfonyl, arylsulfonyl, or lower carbalkoxy containing from one to about ten carbons, acetyl or benzoyl.
- 14. A methine colorant as defined in claim 1 having the formula: ##STR46## wherein: each of R.sub.5 and R.sub.6 is selected from H, alkyl alkoxy, halogen, or trifluoromethyl; and R.sub.18 is phenyl, beta-naphthyl, alpha-naphthyl, thiophenyl, or halothiophenyl.
- 15. A methine colorant as defined in claim 1 having the formula: ##STR47## wherein: each of R.sub.5 and R.sub.6 is selected from H, alkyl, alkoxy, halogen or trifluoromethyl; and R.sub.18 is phenyl, beta-naphthyl, alpha-naphthyl, thiophenyl, or halothiophenyl.
- 16. A methine colorant as defined in claim 1 having the formula ##STR48## wherein: each of R.sub.5 and R.sub.6 is selected from H, alkyl, alkoxy. halogen, or trifluoromethyl; and R.sub.19 is cyano, or lower carbalkoxy containing one to about 10 carbons.
- 17. A methine colorant as defined in claim 1 having the formula: ##STR49## wherein: R.sub.5 is selected from H, alkyl, alkoxy, halogen, or trifluoromethyl; R.sub.11 R.sub.13 and R.sub.14 are each selected from or lower alkyl; and R.sub.19 is cyano or lower carbalkoxy containing one to about ten carbons.
- 18. A methine colorant as defined in claim 1 having the formula: ##STR50## wherein; each of R.sub.5 and R.sub.6 is selected from H, alkyl, alkoxy, halogen, or trifluoromethyl; and R.sub.19 is cyano or lower carbalkoxy containing one to about ten carbons.
- 19. A washable ink composition which comprises an aqueous mixture of water soluble, ester-terminated, poly(alkyleneoxy)-substituted methine colorant of the formula: ##STR51## wherein: AR is an unsubstituted or substituted aromatic or hetero-aromatic group; X is selected from nitrogen or oxygen; R is unsubstituted or substituted straight or branched alkylene of 2-4 carbons or mixtures thereof; R.sub.1 is selected from or an unsubstituted or substituted alkyl, cycloalkyl or phenyl moiety containing one to about 10 carbons, or a group of the formula: ##STR52## wherein R.sub.3 is H or alkyl of one to about ten carbons, and d is zero when X is oxygen and one when X is nitrogen; R.sub.2 is hydrogen or alkyl of one to about five carbons; a and b are each an integer independently selected from one to about forty wherein a+b is an integer of from about 6 to about 80; and Z is a divalent vinylic carbon atom which is covalently bonded to a # group or moiety selected from cyano, vinyl carbon, sulfide, sulfoxide, sulfone, allylic oxygen, thiocyano, or carbonyl which is not part of an amide, carboxylic acid or carboxylic acid salt moiety.
- 20. A composition as defined in claim 19 wherein X is nitrogen.
- 21. A composition as defined in claim 1 wherein X is oxygen.
- 22. A composition as defined in claim 19 wherein the colorant has the formula: ##STR53## wherein: R.sub.5 and R.sub.6 are each selected from hydrogen, alkyl, alkoxy, halogen, or trifluoromethyl; R.sub.8 is selected from cyano, alkylsulfonyl, cycloalkylsulfonyl, arylsulfonyl, or lower carbalkoxy containing one to about ten carbons, acetyl or benzoyl; and R.sub.7 is selected from alkyl, cycloalkyl or unsubstituted or substituted phenyl.
- 23. A composition as defined in claim 19 wherein the colorant has the formula: ##STR54## wherein: R.sub.5 and R.sub.6 are each selected from hydrogen, alkyl, alkoxy, halogen or trifluoromethyl; R.sub.8 is selected from cyano, alkylsulfonyl, cycloalkylsulfonyl, arylsulfonyl, or lower carbalkoxy containing one to about ten carbons, acetyl or benzoyl; and R.sub.7 is selected from alkyl, cycloalkyl or unsubstituted or substituted phenyl.
- 24. A composition as defined in claim 19 wherein the colorant has the formula: ##STR55## wherein: R.sub.5 is selected from H, alkyl, alkoxy, halogen or trifluoromethyl; R.sub.7 is selected from alkyl, cycloalkyl or unsubstituted or substituted pheny; R.sub.8 is selected from cyano, alkylsulfonyl, cycloalkylsulfonyl, arylsulfonyl, or lower carbalkoxy containing from one to about ten carbons, acetyl or benzoyl; and R.sub.11 R.sub.13 and R.sub.14 are each selected from H or lower, alkyl.
- 25. A composition as defined in claim 19 wherein the colorant has the formula: ##STR56## wherein: R.sub.5 and R.sub.6 are each selected from H, alkyl, alkoxy, halogen or trifluoromethyl; and R.sub.15 is selected from H, lower alkyl, phenyl or phenyl substituted with lower alkyl, lower alkoxy or halogen.
- 26. A composition as defined in claim 19 wherein the colorant has the formula: ##STR57## wherein: R.sub.5 and R.sub.6 are each selected from H, alkyl, alkoxy, halogen or trifluoromethyl; and R.sub.15 is selected from H, lower alkyl, phenyl or phenyl substituted with lower alkyl, lower alkoxy or halogen.
- 27. A composition as defined in claim 19 wherein the colorant has the formula: ##STR58## to wherein: R.sub.11, R.sub.13 and R.sub.14 are each selected from or lower alkyl; and R.sub.15 is selected from H, lower alkyl, phenyl or phenyl substituted with lower alkyl, lower alkoxy or halogen.
- 28. A composition as defined in claim 19 wherein the colorant has the formula: ##STR59## wherein: R.sub.5 and R.sub.6 are each selected from H, alkyl, alkoxy, halogen, or trifluoromethyl; and R.sub.16 and R.sub.17 are each selected from oxygen or CR.sub.8 R.sub.8 wherein each R.sub.8 is selected from cyano, alkylsulfonyl, cycloalkylsulfonyl arylsulfonyl, or lower carbalkoxy containing from one to about ten carbons acetyl or benzoyl.
- 29. A composition defined in claim 19 wherein the colorant has the formula: ##STR60## wherein: e is zero, one or two; each R.sub.5 and R.sub.6 is selected from H, alkyl, alkoxy, halogen, or trifluoromethyl; and R.sub.16 is selected from oxygen or CR.sub.8 R.sub.8 wherein each R.sub.8 is selected from cyano, alkylsulfonyl, cycloalkylsulfonyl, arylsulfonyl, or lower carbalkoxy containing from one to about ten carbons, acetyl or benzoyl.
- 30. A composition as defined in claim 19 wherein the colorant has the formula: ##STR61## wherein: R.sub.5 and R.sub.6 are each selected from H, alkyl, alkoxy, halogen, or trifluoromethyl; R.sub.11, R.sub.13 and R.sub.14 are each selected from or lower alkyl; e is 0, 1 or 2; and R.sub.16 is selected from oxygen or CR.sub.8 R.sub.8 wherein each R.sub.8 is selected from cyano, alkylsulfonyl, cycloalkylsulfonyl, arylsulfonyl, or lower carbalkoxy containing from one to about ten carbons, acetyl or benzoyl.
- 31. A composition as defined in claim 19 wherein the colorant has the formula: ##STR62## wherein: each R.sub.5 and R.sub.6 is selected form H, alkyl, alkoxy, halogen, or trifluoromethyl; e is 1, 2 or 3; and R.sub.16 is selected from oxygen or Cr.sub.8 r.sub.8 wherein each R.sub.8 is selected from cyano, alkylsulfonyl, cycloalkyl-sulfonyl arylsulfonyl, or lower carbalkoxy containing from one to about ten carbons, acetyl or benzoyl.
- 32. A composition as defined in claim 19 wherein the colorant has the formula: ##STR63## wherein: each of R.sub.5 and R.sub.6 is selected from H, alkyl, alkoxy, halogen, or trifluoromethyl, and R.sub.18 is phenyl, beta-naphthyl, alpha-naphthyl, thiophenyl, or halothiophenyl.
- 33. A composition defined in claim 19 wherein the colorant has the formula: ##STR64## wherein: each of R.sub.5 and R.sub.6 is selected from H, alkyl, alkoxy, halogen or trifluoromethyl; and R.sub.18 is phenyl, beta-naphthyl, alpha-naphthyl, thiophenyl, or halothiophenyl.
- 34. A composition as defined in claim 19 wherein the colorant has the formula: ##STR65## wherein: each of R.sub.5 and R.sub.6 is selected from H, alkyl, alkoxy, halogen, or trifluoromethyl; and R.sub.19 is cyano, or lower carbalkoxy containing one to about ten carbons.
- 35. A composition as defined in claim 19 wherein the colorant has the formula: ##STR66## wherein: R.sub.5 is selected from H, alkyl, alkoxy, halogen, or trifluoromethyl; R.sub.11, R.sub.13 and R.sub.14 are each selected from H or lower alkyl; and R.sub.19 is cyano or lower carbalkoxy containing one to about ten carbons.
- 36. A composition as defined in claim 19 wherein the colorant has the formula: ##STR67## wherein: each of R.sub.5 and R.sub.6 is selected from H, alkyl, alkoxy, halogen, or trifluoromethyl; and R.sub.19 is cyano or lower carbalkoxy containing one to about ten carbons.
EXPERIMENTAL SECTION
This is a continuation-in-part of application U.S. Ser. No. 07/139,346 filed Dec. 29, 1987 now abandoned.
The present invention relates to methine colorants and to washable ink compositions containing methine colorants. More particularly, the present invention relates to water soluble, ester-terminated, polyalkyleneoxy-substituted methine colorants and to water-based ink compositions containing such colorants having improved washability and stain resistance characteristics.
Washability and resistance to staining are characteristics that may be highly desirable in a wide variety of end use applications for inks, especially in applications designed for young children. Such applications may include, for instance, water colors, inks for "nib-type" pens as well as felt-type and wick markers, stamp pads, recording pens and a wide variety of other applications that will be readily apparent to those skilled in this art.
Conventional, water-based inks designed, for instance, for use in marker pens sold primarily for use by young children may typically consist of very fine pigment dispersions in aqueous media which may contain a minor amount of a solvent such as glycol, polyols, polyoxyethers, or other functionalized alcohols and a dispersing agent. Alternatively, such marking ink compositions may be comprised of conventional acid, e.g., dyes containing sulfonic acid groups or their corresponding salts, dyestuffs in an aqueous glycerine solution.
Such conventional ink compositions are characterized by certain serious disadvantages, especially where use by children is contemplated. Thus, such inks may stain the skin and clothing of the user and may not be easily removable using conventional procedures for washing hands or laundering clothing. Certain low molecular weight acid dyes may not be desirable for use in ink compositions since they are suspected carcinogens. Many of the solvents conventionally found in such ink compositions may also have an objectionable odor, and they may also be toxic, (upon inhalation or skin contact), and are therefore undesirable for use in inks for those reasons as well (see Polymers, Paint, Color Journal, Vol. 177, No. 4192, 1987). Furthermore, many of the conventional ink compositions may not be stable upon storage because the pigment or dyestuff may precipitate from the ink composition with the passage of time.
Accordingly, the ink compositions of the present invention may overcome all or many of the disadvantages found in conventional ink compositions. In particular the ink compositions of the invention may exhibit improved resistance to staining of both skin and fabrics including one or more of cotton, wool, acetate, polyester, polyamide, acrylics, silk and viscose so that all, or virtually all of the colorant may be removed from skin by means of conventional soap and water washing and from clothing using normal laundering techniques. Furthermore, the ink compositions of the present invention have exceptional tinctorial power, exhibit superior brightness, and may be less toxic to humans due to the relatively high molecular weight of the colorant and because other solvents may not necessarily be present in the ink compositions.
The ink compositions of the present invention exhibit excellent brilliance, intensity and clarity of color especially when used on paper substrates. In addition, the present ink compositions may be applied smoothly and uniformly from a typical writing or marking instrument onto a wide variety of substrate surfaces. Once applied to a given substrate the ink compositions are also not undesirably transferred from the intended substrate such as paper to other objects such as clothing or skin by, for instance, sublimation as may occur with conventional inks even after drying because they contain lower molecular weight, more volatile colorants.
Accordingly, the present invention provides:
A washable ink composition which comprises an aqueous mixture of a alkyleneoxy-substituted methine colorant of the formula: ##STR3## wherein: AR is an unsubstituted or substituted aromatic or hetero-aromatic group; X is selected from nitrogen or oxygen; R is unsubstituted or substituted straight or branced alkylene of 2-4 carbons or mixtures thereof; R.sub.1 is selected from or an unsubstituted or substituted alkyl cycloalkyl or phenyl moiety containing one to about 10 carbons, or a group of the formula ##STR4## wherein R.sub.3 is or alkyl of one to about ten carbons, and d is zero when X is oxygen and one when X is nitrogen; R.sub.2 is hydrogen or alkyl of one to about five carbons; a and b are each an integer independently selected from one to about forty wherein a+b is an integer of from about 6 to about 80 and z is a divalent vinylic carbon atom which is covalently bonded to a group or moiety selected from cyano, vinyl carbon, sulfide, sulfoxide, sulfone, allylic oxygen, thiocyano, or carbonyl which is not part of an amide, carboxylic acid or carboxylic acid salt moiety.
It is to be understood that in the structural formula set forth above and in the claims the representation of the alkylene oxide portion of the molecule may include, e.g., ethylene oxide homopolymers as well as copolymers of ethylene oxide and higher order alkoxydes such as propylene oxide especially random copolymers and block copolymers.
The present invention also relates to certain methine colorants of the type set forth in formula I above wherein all of the values given for the various substituents are as set forth above exept that the sum of a+b may be from about 6 to about 80. In addition to their utility for use in making washable ink compositions the methine colorants may be useful in a wide variety of other end use applications, for instance as reactive coloring agents for polyurethanes and other polymers, as colorants for certain thermoplastic polymers, such as polyolefins, polyesters, etc., as markers for agricultural chemicals and as fugitive tints for textile applications.
In general methine colorants are well known chemical compounds having a wide range of end use applications including, for instance, their uses as dyestuffs in coloring cellulose triacetate, polyamide, polyester, and polyurethane substrates. More recently they have been suggested for use as U.V. absorbers which impart ultraviolet screening properties to numerous water-soluble, ester-terminated, polyalkyleneoxy-substituted methine colorants been disclosed or suggested. Neither has there been any suggestion in the art of washable ink compositions containing such methine colorants.
Colorants made of polyalkyleneoxy-substituted chromophores are also known and have been disclosed as having utility, for instance as fugitive tints in coding fabrics of different types for identification purposes prior to textile processing.
Such compounds have, for instance, been disclosed in U.S. Pat. No. 3,157,663 to Kuhn. While such colorants are water soluble and homogeneous, they are not suitable for washable ink compositions for several reasons. The corresponding colorants of Kuhn, as mentioned above, are used primarily to tint fabric substrates; therefore, they are usually of very high molecular weight units containing as many as 100 to 200 ethylene oxide units. Such compounds may be in a solid phase at standard temperatures and pressure and may have poor tinctorial properties (very low color strength). Since an aqueous ink composition requires water as the solvent for the polymeric colorant as well as any potential other additives, compositions as disclosed above require extremely high loadings of solid polymeric colorants to be dissolved in water. This inherent property leads to ink compositions of polymeric colorants with very little water and exceedingly high concentrations of polymeric colorants which in turn leads to ink compositions of unacceptably high working viscosities. In many cases, an ink composition cannot even be prepared with high enough color strength to be useful in the washable marker area of the present invention. The ink compositions of the present invention, by contract contain colorants as defined above, such that the ink has high color strength and low solution viscosity (required in ink compositions) while maintaining its washability and non-staining characteristics. A viscosity of from 6 to about 1 centipoises is desirable. Preferably the viscosity may be less than about 5 centipoises. Viscosity is measured by a Model LVT Brookfield viscosimeter, UL adapter at 60 RPM's.
A typical preferred ink composition of the present invention is compried of from about 40 percent by weight to about 80 percent by weight of water; from about 10 percent by weight to about 50 percent by weight of alkyleneoxy-substituted methine colorant containing from about 10 percent by weight to about 50 percent by weight of polyalkylene oxide units. The polymeric colorants selected for he washable ink compositions of the present invention contain from about 5 percent by weight to 40 percent by weight of polyalkylene oxide; wherein the alkylene oxide is preferably ethylene oxide.
In addition to the ester-terminated, polyalkyleneoxy-substituted methine colorant component and water which serves as a solvent for the ink composition, a wide variety of additives may also be employed to impart specific properties to the ink composition in either the wet or dried state. Some common additives which may be present include, for example, organic components which are well known in the art and which function as humectants, biocides, and chelatings agents.
Any humectant having water solubility can be used in the ink composition of this invention and where the composition is employed in a marker pen; for instance, it may serve to substantially prevent or minimize the marker tip from drying. Several examples of humectants commercially used are glycerine, diethylene glycol and polyethylene glycols, and sorbitol. The percent by weight of humectants can vary but typically about 5 to about 20 percent by weight of the ink composition is used.
A biocide or bactericide can be added to improve shelf-life of the ink composition. Biocides which are particularly useful in the composition are Nuosept and both methyl and propyl parasepts. The biocide retards the growth of micro-organisms which may degrade the ink and can be eliminated if it is not necessary to inhibit the growth of bacteria. The biocide therefore adds to the shelf-life of the ink composition. In general, the percentage by weight of biocide can vary greatly depending on the chemical nature of biodice, however, from 0.02 to about 0.5 percent by weight have been found to be generally useful. Some commercially available biocides that can be utilized are as follows: Troysan Polyphase AF-1, Troysan 174, Troysan 142, Cosan 101, Amical 48, Tektamer 38 A.D., Dowicil 75, Metasol TK 100 Dispersion W, Omacide 50, Acticide APA, Domiphen Bromide, Benzalonium Chloride, Cetyl Pyridium Chloride, Kathon CG/ICP/886 MW 1.5% LX, Euxyl K1OO, and Glutaraldehyde.
Various chelating agents may be provided in the ink composition to improve shelf-life. Thus, for instance, EDTA is a chelating agent which complexes metal ions such as iron, zinc, magnesium, etc. and prevents the precipitation of these metal ions. The percentage by weight of metal chelating can vary greatly, however, generally from 0.1 to about 0.5 percent by weight of EDTA (sodium salt) on the weight of the total ink composition can be employed to prevent the formation of water insoluble carbonate salts when the ink compositions is exposed to ambient air which contains carbon dioxide.
Another aspect of shelf-life is the maintenance of the polyalkyleneoxy colorant and this is extended by maintaining the pH of the ink at some value close to about 7.0. The pH can go below about 6.5 without loss of activity. However, values of pH above 8.0 can severely degrade the colorant especially if elevated temperatures are involved. Accordingly, the pH of the ink composition is adjusted to from about 5.5 to about 8.0 and preferably from about 6.5 to about 7.5.
As mentioned above, the ink compositions of the present invention are characterized by significantly reduced staining of fabrics. Fabric staining may be determined by measuring the delta E*ab value of the residual colorant stain. This delta E*ab value is directly related to fabric staining after laundering. The numberical value of delta E*ab as is determined in this invention can vary from 0 to about 10; preferably from 0 to about 5.
In addition, the ink compositions also are characterized by significantly reduced staining of skin. Skin staining may be measured by rating the residual skin stain after washing the hands with soap and water. The numerical value for hand staining, on a scale of zero to ten, as determined in this invention can vary from 0 to about 2; preferably from 0 to about 1.
The following examples serve to illustrate the subject matter of the present invention and are not to be construed as limiting the scope of the invention. All parts and percentages which are set forth are by weight unless otherwise indicated. The following abbreviations are utilized in the following tables Et=ethyl; Me=methyl; EO=ethylene oxide unit; PO=propylene oxide; Ac=Acetate; and DiAc=Diacetate.
US Referenced Citations (4)
| Number |
Name |
Date |
Kind |
|
3846141 |
Ostergren et al. |
Nov 1974 |
|
|
4167510 |
Brendle |
Sep 1979 |
|
|
4703113 |
Baxter et al. |
Nov 1987 |
|
|
4877411 |
Hines et al. |
Oct 1989 |
|
Continuation in Parts (1)
|
Number |
Date |
Country |
| Parent |
139346 |
Dec 1987 |
|
Patent Grant
4981516
