JPH0526672B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of the Invention] The present invention relates to a coating agent for cationic dye dry transfer coloring and a method for manufacturing articles using the same, and relates to a cationic dye that is easily dyed with a sublimable cationic dye and has excellent coloring properties and vividness. The present invention relates to a coating agent for dry coloring and a method for manufacturing articles using the same. [Technical background of the invention and its problems] With the recent rapid spread of office automation, the use of color displays has rapidly increased in personal computers, word processors, office computers, etc., which are the core of office automation. There is a rapidly increasing demand for practical use of recording methods, and there is also a strong demand for colorization in the field of dry copying machines. Conventional color recording methods include a thermal transfer method, an inkjet method, a wire dot method, and the like. Among these color recording methods, the thermal transfer method is particularly promising because it does not generate sound and the copying machine is easy to handle, maintain, and manage. However, the current thermal transfer method is a dry transfer coloring technology using sublimable disperse dyes on synthetic fiber paper or synthetic resin film, which has drawbacks such as lack of dry transfer coloring properties and sharpness of color tone due to disperse dyes. There was a strong demand for improvement. [Object of the Invention] The object of the present invention is to provide a coating agent for cationic dye dry transfer coloring that is easily dyed with a sublimable cationic dye and has excellent coloring properties and vividness, and a method for manufacturing articles using the same. It's about doing. [Summary of the Invention] As a result of intensive research to achieve the above-mentioned object, the present inventors have developed a compound having dicite that can be dyed with a specific cationic dye on paper, film, etc.
Or a mixture of a phosphoric acid ester monomer and an amine compound: 1 to 40% by weight of a polyoxyalkylene compound based on the active energy ray-curable resin: Apply a coating agent made of a specific resin.
The present invention was completed based on the discovery that, when cured, the paper/film can be easily dyed with a sublimable cationic dye, and the dye has excellent color development and clarity. That is, the coating agent for cationic dye dry transfer coloring of the present invention comprises: an active energy ray-curable resin; (a) a compound having a cationic dye-dyeable dicite; or (b) a compound having a cationic dye-dyable dicite; , general formula; [In the formula, at least one X is a general formula; (In the formula, R ₁ represents a hydrogen atom or a methyl group,
_R2 represents an alkylene group having 1 to 10 carbon atoms, and n is an integer of 0 to 10. ), and the remainder represents a hydroxyl group. ] A phosphoric acid ester monomer represented by the general formula; [Wherein, at least one Y is a general formula; H-( _OR3 ) _n --(wherein, _R3 represents an alkylene group having 1 to 10 carbon atoms, and m is an integer of 1 to 10 ) and the remainder represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]
or (c) a mixture of a phosphoric acid ester monomer represented by the above formula () and an amine compound represented by the above formula (): to the active energy ray-curable resin. On the other hand, 1~
_{40 %} by weight _{of the} following general formula _{( )} ; represents,
R ₁₁ represents an alkylene group having 2 to 6 carbon atoms, and q is an integer of 5 to 30. ), and the following general formula (); (In the formula, R ₄ represents a hydrogen atom or a methyl group,
R ₅ represents an alkylene group having 2 to 6 carbon atoms,
R ₆ represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acryloyloxy group, or a methacryloyloxy group, and p is an integer of 13 to 30. ) It is characterized by consisting of at least one kind selected from the group consisting of polyoxyalkylene compounds shown in the following. The active energy ray-curable resin used in the present invention may be any resin as long as it is curable with active energy rays (e.g., ultraviolet light), such as photodimerizable resins such as polyvinyl cinnamic acid. Resin; unsaturated polyester type, polyether acrylate or polyether methacrylate type (hereinafter, ``acrylate or methacrylate'' is simply abbreviated as ``(meth)acrylate''), polyester (meth)acrylate type, polyol (meth)acrylate type photo-initiated radical polymerization type resins such as epoxy (meth)acrylates, amide urethane (meth)acrylates, urethane (meth)acrylates, spiroacetal (meth)acrylates, and polybutadiene (meth)acrylates; epoxy resins Examples include photocationic polymerizable resins such as. The active energy ray-curable resin preferably has
It consists of at least one selected from the group consisting of monomers and oligomers, or it consists of a mixture of a polymer and at least one selected from the group consisting of monomers and oligomers. Specific examples of such active energy ray-curable resin monomers or oligomers include 1,
2-propylene glycol/phthalic anhydride/maleic anhydride, ethylene glycol/terephthalic acid/maleic anhydride, 1,4-butanediol/
Unsaturated polyesters synthesized from tetrahydrophthalic anhydride/fumaric acid, etc.; 1,2,6-hexanetriol/propylene oxide/acrylic acid, trimethylolpropane/ethylene oxide/methacrylic acid, trimethylolpropane/propylene oxide/acrylic acid, Polyether (meth)acrylate synthesized from pentaerythritol/ethylene oxide/acrylic acid; adipic acid/1,6-hexanediol/acrylic acid, succinic acid/1,4-butanediol/acrylic acid, succinic acid/trimethylolethane /acrylic acid, sebacic acid/1,6-hexanediol/
Polyester (meth)acrylate synthesized from methacrylic acid, etc.; ethylene glycol diacrylate, triethylene glycol diacrylate, ethylene glycol dimethacrylate, hexapropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,6 -hexanediol diacrylate, 1,4-butanediol dimethacrylate, butyl acrylate, 2-
Ethylhexyl acrylate, lauryl methacrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethyl methacrylate, 1,4-butanediol monoacrylate, benzyl methacrylate, ethylene carbitol acrylate, trimethylolpropane triacrylate, trimethylolethane trimethacrylate, penta Erythritol pentaacrylate, pentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexamethacrylate, 2,2-bis(4-acryloyloxyethoxyphenyl)propane, 2,2-bis(4) -acryloyloxydiethoxyphenyl)
(Meth)acrylate or polyol (meth)acrylate such as propane, 2,2-bis(4-methacryloyloxydiethoxyphenyl)propane, 2,2-bis(4-acryloyloxypropoxyphenyl)propane; diglycidyl ether bisphenol A/acrylic acid, diglycidyl etherified polybisphenol A/acrylic acid, triglycidyl etherified glycerin/acrylic acid, triglycidyl etherified trimethylolethane/methacrylic acid, diglycidyl etherified aniline/acrylic acid, etc. Epoxy (meth)acrylate; γ-butyrolactone/N-methylethanolamine/bis(4-isocyanatocyclohexyl)methane/2-hydroxyethyl acrylate, γ-butyrolactone/N-methylethanolamine/2,6-tolylene diisocyanate/ Amide urethane (meth) such as tetraethylene glycol/2-hydroxyethyl acrylate
Acrylate; Urethane acrylates such as 2,6-tolylene diisocyanate diacrylate, isophorone diisocyanate diacrylate, isophorone diisocyanate dimethacrylate, urethane acrylate synthesized from hexanediol/isophorone diisocyanate/2-hydroxyethyl acrylate, hexamethylene diisocyanate diacrylate; Spiroacetal acrylate synthesized from diarylidene pentaerythritol/2-hydroxyethyl acrylate;
Acrylated polybutadiene synthesized from epoxidized butadiene/2-hydroxyethyl acrylate; polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol glycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether,
Epoxy resins such as pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether, diglycidyl etherified bisphenol A, diglycidyl etherified polybisphenol A, diglycidyl etherified aniline; trisacryloyloxyethyl isocyanurate, etc. These monomers and oligomers may be used alone or in combination of two or more. The monomers, oligomers and polymers preferably have an average number of polymerizable groups or epoxy groups of more than one per molecule, and more preferably have an average number of polymerizable groups or epoxy groups of more than 1 per molecule.
It is preferable that the number exceeds 1.5. If the number of bases is less than one, the curing properties of the coating agent may be poor or the blocking properties between coated articles may be poor. In particular, the polymer contains 0 to 30% by weight of the active energy ray-curable resin, and the number of at least one polymerizable unsaturated group or epoxy group selected from the group consisting of monomers and oligomers is on average per molecule. It is preferable that there are 1.5 or more. In this case, the coated article has good scratch resistance;
It is more desirable because it is less likely to be damaged during handling and the color-copied article can maintain its beauty forever. Furthermore, the general formula for oligomers is: [In the formula, N is an integer from 1 to 4, and at least 3 or more Xs are represented by the general formula: (In the formula, R ₇ represents a hydrogen atom or a methyl group,
R ₈ represents a single bond, an alkylene group having 1 to 8 carbon atoms, or a polyoxyalkylene group having an alkylene group having 1 to 8 carbon atoms. ), the remainder being an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, the formula: -(OR ₉ ) _M -H (in the formula,
R ₉ represents an alkylene group having 1 to 8 carbon atoms,
M is a positive integer. ) Group or formula represented by: -(
OR ₉ ) _M ---OH (in the formula, R ₉ and M have the same meanings as above); ] Also preferable are those containing 10% by weight or more of the compound represented by the formula. This is because when such a compound is contained in an amount of 10% by weight or more, active energy ray curing properties in the air are improved, and coating workability is improved. Specific examples of this compound include dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol pentaacrylate, tripentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, and the like. When a polymer is used in combination with at least one selected from the group consisting of monomers and oligomers,
Any material may be used as long as it has film-forming ability, and examples thereof include polyamide, polyester, polyvinyl acetate, acrylic resin, cellulose resin, and the like. When these polymers are used, at least 10% by weight of the active energy ray-curable resin is composed of at least one member selected from the group consisting of monomers and oligomers in order to prevent blocking between coated articles. It is desirable to use a resin consisting of: The compound having a cationic dye-dyeable dicite (dyeable site) used in the present invention is not particularly limited as long as it can be dyed with a cationic dye.
Specific examples of compounds having dicite include dodecylbenzenesulfonic acid triethanolamine salt, octadecylbenzenesulfonic acid triethanolamine salt, 2-(styrene)glycine, acrylamide, acrylic acid, methacrylic acid, acrylonitrile, and methyleneglutaronitrile. , 2-
Dimethylaminoethyl methacrylate, sodium 5-sulfonate isophthalate, 2-acrylamido-2-methylpropanesulfonic acid, sodium 2-methacrylethanesulfonate, sodium 3-methacrylpropanesulfonate, sodium 2-propenesulfonate, 2- Methyl-2-
Sodium propene sulfonate, sulfoethyl acrylate, sulfoethyl methacrylate, sulfobutyl acrylate, sulfoethyl vinyl acetate, sulfopropyl vinyl propionate,
Examples include 2-methacrylamido-2-methylpropanesulfonic acid and 3-acrylamido-3-methylbutanesulfonic acid, and one or more selected from the group consisting of these are used. In order to dye strongly with cationic dyes,
The dicite is preferably a sulfonic acid group or a compound having a sulfonic acid group, and considering the polymerizability with active energy rays and the solidity of dyeing due to the immobilization of the dyeable dicite, the polymerizable group is an acryloyl group or a compound having a sulfonic acid group. More preferred are compounds having a methacryloyl group. Moreover, when it has such a polymerizable group, it may be a copolymer with other monomers. As the sulfonic acid base, a sulfonic acid ammonium salt type sulfonic acid base is most preferable because it has good dry transfer coloring properties. Examples of ammonium sulfonate salts include 2
-Acrylamido-2-methylpropanesulfonic acid ammonium salt, 2-methacrylethanesulfonic acid ammonium salt, 3-methacrylpropanesulfonic acid ammonium salt, 2-methacrylamido-2-methylpropanesulfonic acid ammonium salt, and the like. These ammonium salt type monomers may be used as they are, or after curing a coating agent containing a monomer having a sulfonic acid group or a sodium sulfonate group, an inorganic acid ammonium salt may be used. It may also be used as an ammonium salt type monomer obtained by immersing it in an aqueous solution containing a salt and heat-treating it. The ammonium salt of the inorganic acid is not particularly limited as long as it can convert the sulfonic acid group of dicite into an ammonium salt type salt. Specific examples of this ammonium salt include ammonium sulfate, ammonium chloride, ammonium sulfamate, and the like. The concentration of this ammonium salt is equal to or higher than the sulfonic acid group or sodium sulfonate group of the monomer, and the treatment temperature is 80°C.
~140°C and a treatment time of several minutes to several tens of minutes is desirable. The phosphate ester monomer used in the present invention is
This is a compound represented by the general formula () described above.
Specific examples of this compound include acryloyloxyethyl phosphate, methacryloyloxyethyl phosphate, acryloyloxypropyl phosphate, methacryloyloxybutyl phosphate, acryloyloxydiethoxy phosphate, methacryloyloxytriethoxy phosphate. ate, diacryloyloxyethyl phosphate, dimethacryloyloxyethyl phosphate, diacryloyloxydiethoxy phosphate, and the like. In addition,
Other examples of this compound include halogenated vinyl phosphates and alkyl-substituted vinyl phosphates, but these are not preferred because they do not have sufficient curing properties with active energy rays. The amine compound used in the present invention is a compound represented by the general formula () described above. Specific examples of this compound include ethanolamine, diethanolamine, dimethylethanolamine, diethylethanolamine, ethyldiethanolamine,
Di-n-hexylethanolamine, n-hexyldiethanolamine, β-ethylhexylethanolamine, n-butyldiethanolamine,
n-lauryldiethanolamine, n-cetyldiethanolamine, triethanolamine, n-
Examples include lauryldiethanolethoxyamine and n-lauryldiethanolpropoxyamine. A compound having a cationic dye-dyeable dicite or a mixture of a cationic dye-dyable dicite-containing compound, a phosphate ester monomer, and an amine compound used in the coating agent of the present invention;
Alternatively, the blending ratio of the mixture of the phosphoric acid ester monomer and the amine compound is in the range of 0.1 to 30% by weight, preferably in the range of 1 to 25% by weight, based on the active energy ray-curable resin. If this blending ratio is less than 0.1% by weight, the dyeing density with the cationic dye will not be sufficient, and if it exceeds 30% by weight, the compatibility or dispersibility with the active energy ray-curable resin will be poor. In addition, the compounding ratio of the compound having cationic dye-dyeable dicite, the phosphoric acid ester monomer, and the amine compound is usually 1/4 to 4/1 by weight.
is within the range of Furthermore, the molar ratio of the phosphoric acid ester monomer and the amine compound is usually in the range of 1/4 to 4/1. If it deviates from these ranges, the dyeability of the cationic dye will deteriorate. These phosphate ester monomers and amine compounds may be independently blended into the active energy ray-curable resin, or they may be obtained by reacting both the phosphate monomer and the amine compound in advance. An additional compound may be added to the active energy ray-curable resin. This addition compound acts as a dicite for cationic dyes. Note that it is not possible to improve the dyeing properties of sublimable dyes for cationic dye dry transfer coloring using only either the phosphoric acid ester monomer or the amine compound. Specific examples of polyoxyalkylene compounds used in the present invention include diethylene glycol, triethylene glycol, pentaethylene glycol,
Octaethylene glycol, dodecaethylene glycol, tripropylene glycol, octapropylene glycol, decapropylene glycol,
Methoxytetraethylene glycol, methoxytetradecapropylene glycol, hexaethylene glycol acrylate, methoxytridecaethylene glycol acrylate, tricosaethylene glycol diacrylate, octadecapropylene glycol diacrylate, etc., were selected from the group consisting of these. One or more types may be used. Among these polyalkylene oxide compounds, considering the relaxation effect of these compounds, the general formula (): R ₉ - (OR ₁₁ ) _q - OR ₁₀ () (wherein R ₉ and R ₁₀ are each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
R ₁₁ represents an alkylene group having 2 to 6 carbon atoms, and q is an integer of 5 to 30. ) is preferred; when a large amount of these compounds is blended, the tackiness increases or the scratch resistance decreases due to bleed-out, so the general formula: (In the formula, R ₄ represents a hydrogen atom or a methyl group,
R ₅ represents an alkylene group having 2 to 6 carbon atoms,
R ₆ is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms,
It represents an acryloyloxy group or a methacryloyloxy group, and p is an integer of 13 to 30. ) Compounds having a polymerizable group are more preferred. Specific examples of the polyoxyalkylene compound having the polymerizable group described above include hexaethylene glycol acrylate, methoxytridecaethylene glycol methacrylate, tricosaethylene glycol diacrylate, octadecapropylene glycol diacrylate, nonaethylene glycol acrylate, Examples include nonaethylene glycol dimethacrylate, tricosaethylene glycol dimethacrylate, tetradecapropylene glycol acrylate, and tetradecapropylene glycol diacrylate. The blending ratio of the polyoxyalkylene compound used in the coating agent of the present invention is in the range of 1 to 40% by weight, preferably in the range of 5 to 30% by weight, based on the active energy ray-curable resin. If this blending ratio is less than 1% by weight, the dyeing promotion effect of the cationic dye will not be sufficient, and if it exceeds 40% by weight, the coating film will become sticky due to bleeding of the polyoxyalkylene compound or the light resistance will be poor. becomes. The coating agent of the present invention may include, if necessary,
As other components, a photoinitiator, a photosensitizer, a mixture of these and a co-catalyst, etc. may be blended. Specific examples of these photoinitiators, photosensitizers, and mixtures of these and cocatalysts include benzoin, benzoin isobutyl ether, benzyl dimethyl ketal, and ethyl phenyl glyoxylate for photoinitiated radical polymerization type resins. , diethoxyacetophenone, 1,1-dichloroacetophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, benzophenone/diethanolamine, 4,4' -bisdimethylaminobenzophenone, 2-methylthioxanthone,
Carbonyl compounds such as tert-butylanthraquinone and benzyl; Sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; Azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile ; Peroxide compounds such as benzoyl peroxide and di-tert-butyl peroxide;
Epoxy resins include aryldiazonium compounds such as phenyldiazonium tetrafluoroborate and 4-methylphenylhexafluorophosphate; 4,4'-dimethyldiphenyliodonium hexafluorophosphate and diphenyliodonium hexafluoroarsenate. diaryliodonium compounds such as; triarylsulfonium compounds such as triphenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluoroarsenate; these compounds can be used alone or in a mixed system of two or more. be done. The blending ratio of these compounds is usually 0.01 to the coating agent for cationic dye dry transfer coloring.
~10% by weight, preferably 0.01% by weight
The range is less than or equal to If this blending ratio is out of the above-mentioned range, the coating may be colored or the light resistance may be decreased, which is not preferable. The present invention also provides a method for producing a novel cationic dye dry transfer coloring article. That is, the method for producing an article for cationic dye dry transfer coloring of the present invention includes the above-mentioned active energy ray-curable resin and: (a) a compound having cationic dye-dyeable dicite; or (b) a cationic dye-dyeable dicite-containing A compound having a general formula; (In the formula, R ₁ represents a hydrogen atom or a methyl group,
_R2 represents an alkylene group having 1 to 10 carbon atoms, and n is an integer of 0 to 10. ), and the remainder represents a hydroxyl group. ] A phosphoric acid ester monomer represented by the general formula; [Wherein, at least one Y is a general formula; H-( _OR3 ) _n --(wherein, _R3 represents an alkylene group having 1 to 10 carbon atoms, and m is an integer of 1 to 10 ) and the remainder represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]
or (c) a mixture of a phosphoric acid ester monomer represented by the above formula () and an amine compound represented by the above formula (): to the active energy ray-curable resin. On the other hand, 1~
_{40 %} by weight _{of the} following general formula _{( )} ; represents,
R ₁₁ represents an alkylene group having 2 to 6 carbon atoms, and q is an integer of 5 to 30. ), and the following general formula (); (In the formula, R ₄ represents a hydrogen atom or a methyl group,
R ₅ represents an alkylene group having 2 to 6 carbon atoms,
R ₆ represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acryloyloxy group, or a methacryloyloxy group, and p is an integer of 13 to 30. ) A coating agent selected from the group consisting of polyoxyalkylene compounds represented by the following is applied to the surface of a film or paper, and then cured with active energy rays. The film or paper used in the production method of the present invention may be any film or paper that is normally used as a base material for dry transfer. Specific examples of films and papers include polyester film, propylene film, nylon film,
Film-like materials such as vinyl chloride film; paper-like materials such as art paper made mainly of wood fibers, acrylic paper made mainly of acrylic fibers, and polyester paper; especially polyester films when heat resistance is taken into consideration. Alternatively, acrylic paper or art paper is preferable, and polyester film is most preferable in consideration of the transparency of the article. These papers or films may be used as they are, or may be washed, etched, corona discharged, irradiated with active energy rays, dyed,
You may use one that has been subjected to pretreatment such as printing. In the method of the present invention, first, the coating agent of the present invention is usually mixed uniformly in advance and applied to the surface of paper/film. At the time of mixing or coating, a solvent may be used in combination depending on the paper/film, and this combination of solvents may be desirable in consideration of the workability of coating. Examples of the coating method include a spray method, a roll coater method, a gravure coating method, a dip method, and a flow coating method. Next, the coating film on the paper/film is cured with active energy rays. As active energy rays, xenon lamps,
Ultraviolet rays emitted from sources such as low-pressure mercury lamps, high-pressure mercury lamps, or ultra-high-pressure mercury lamps, electron beams extracted from electron beam accelerators of usually 20 to 2000 kV, alpha rays and beta rays.
Examples include radiation such as rays and gamma rays, and ultraviolet rays in the wavelength range of 100 to 800 nm are preferable in consideration of handling and workability. When using ultraviolet rays as active energy rays, it is better to add to the coating agent a photoinitiator, a photosensitizer, and a mixture of these and a co-catalyst that can initiate a polymerization reaction upon irradiation with ultraviolet rays to improve curing properties. It is preferable in terms of. [Effects of the Invention] The cationic dye dry transfer coloring coating agent of the present invention is easily dyed with a sublimable cationic dye, and has significantly superior coloring properties and vividness compared to conventional ones. In addition, the article obtained by the manufacturing method of the present invention using this coating agent has the above-mentioned excellent properties, has high heat resistance, and can perform dry transfer of cationic dye at low temperature and in a short time. . Therefore, the coating agent of the present invention and the article according to the present invention are extremely useful as, for example, dry transfer coloring materials for color copying, electrophotography, or information recording.
Its industrial value is great. [Embodiments of the Invention] Examples of the present invention will be listed below and will be described in more detail. In addition, in the examples and comparative examples, "part"
All numbers are parts by weight. Examples 1 to 4 The cationic dye dry transfer color forming coating agent of the present invention having the composition shown in the table was diluted with the mixed solvent shown in the table and stirred to prepare a coating agent coating liquid. Next, a polyester film (thickness: 100 μm) was continuously immersed in this coating agent coating solution.
It was pulled up at a speed of cm/sec, left for a certain period of time, and then irradiated with ultraviolet rays in an air atmosphere to obtain an article according to the manufacturing method of the present invention. In Example 2, the film of Example 1 was further treated with 10 ammonium sulfate.
A moist heat treatment was performed for 30 minutes in an aqueous solution at 98°C containing g/g/. Evaluation tests for this article were conducted in the following manner. (1) Measurement of cationic dye dry transfer color development Using a Husing Press Model XVOB6.5/14 (manufactured by Carnegisser), place cationic dye transfer paper (manufactured by Dai Nippon Printing Co., Ltd., blue) on the surface of the article, and touch it. Dry transfer printing was carried out under the conditions of a pressure of 2 Kg/cm ² , a temperature of 180° C., and a time of 5 seconds. Next, the Y value was measured using Color Analyzer Model 307 (manufactured by Hitachi, Ltd.), and the K/S value was calculated by substituting the Y value into Kubelkamunk's equation below, and the values were summarized in a table as an evaluation of color development. Shown. K/S=(1-R) ² /2R (In the formula, R=Y value/100.) (2) Scratch resistance Lightly scratch the surface of the article with #0000 steel wool and check the degree of scratches. Observed. The results are shown in the table.
In the table, those with few scratches are indicated as "good".
Those with noticeable scratches were designated as "defect". (3) Blocking resistance Evaluation was made by stacking articles, applying appropriate pressure, and then peeling off the articles. The results are shown in Table 2.
In the table, items that could be easily peeled off from each other were designated as "good", and items that were sticky and required some force were designated as "poor". Comparative Examples 1 to 2 The coating agent for cationic dye dry transfer color development of the present invention having the composition shown in the table was diluted with the mixed solvent shown in the table and stirred to prepare a coating agent coating liquid. Next, articles of comparative examples were obtained in the same manner as in the examples.
Regarding the obtained articles, evaluation tests similar to those in Examples were conducted. The results are shown in the table.

【table】

[Table] Example 5 60 parts of acrylic copolymer consisting of methyl methacrylate/ethyl acrylate (70/30), 8 parts of dipentaerythritol hexaacrylate, 5 parts of dipentaerythritol pentaacrylate,
Dipentaerythritol tetraacrylate 5
parts, 9 parts of tetradecapropylene glycol diacrylate, 3 parts of 2-methacrylamido-2-methylpropanesulfonic acid, 3 parts of bisacryloxyethyl phosphate, 2 parts of n-lauryldiethanolamine, 2-hydroxy-2-methylpropylene The cationic dye dry transfer coloring coating agent of the present invention consisting of 5 parts of ofenone was mixed with 400 parts of toluene and 400 parts of toluene.
100 parts dimethylformamide, isopropanol
A coating agent coating liquid was prepared by diluting and stirring with a mixed solvent of 200 parts of isobutanol and 200 parts of isobutanol. Next, a corona discharge-treated polyester film (thickness: 100 μm) was continuously immersed in this coating solution, pulled up at a speed of 1 cm/sec, and left to stand for a certain period of time. The coating film was cured by irradiation to obtain an article according to the manufacturing method of the present invention. The obtained article was subjected to the same evaluation test as in Example 1, and the results showed that the cationic dye dry transfer color development was good and K/
S=8.8. In addition, the scratch resistance was moderate. Example 6 Icosaethylene glycol diacrylate 15
15 parts of urethane acrylate consisting of polycaprolactone diol/isophorone diisocyanate/2-hydroxyethyl acrylate, 8 parts of dipentaerythritol pentaacrylate, 7 parts of dipentaerythritol hexaacrylate,
20 parts of tetrahydrofurfuryl acrylate, 10 parts of ethylhexyl acrylate, adipic acid/1,
9 parts of polyester acrylate consisting of 6-hexanediol/acrylic acid, 3 parts of 2-acrylethanesulfonic acid, 4 parts of methacryloxyethyl phosphate, 2 parts of n-butyldiethanolamine
1 part of 2-hydroxy-2-methylpropiophenone, the coating agent for cationic dye dry transfer coloring of the present invention is diluted with a mixed solvent of 200 parts of xylene, 120 parts of isopropanol and 80 parts of dimethylformamide, and stirred. A coating agent coating solution was prepared. Next, a polyester film (thickness: 100μ) is continuously immersed in this coating agent coating liquid at a speed of 1.5 cm/sec, pulled out, left to stand, and then irradiated with ultraviolet rays in the air to produce a film according to the manufacturing method of the present invention. Obtained goods. The obtained article was subjected to the same evaluation test as in Example 1, and as a result, the dyeability by cationic dye dry transfer printing was good, with K/S = 9.5.
In addition, blocking resistance and scratch resistance were also good.

Claims (1)

[Scope of Claims] 1 An active energy ray-curable resin: (a) a compound having a cationic dye-dyeable dicite, or (b) a compound having a cationic dye-dyeable dicite, and a general formula; [In the formula, at least one X is a general formula; (In the formula, R ₁ represents a hydrogen atom or a methyl group,
_R2 represents an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 10. ), and the remainder represents a hydroxyl group. ] A phosphoric acid ester monomer represented by the general formula; [Wherein, at least one Y is a general formula; H-( _OR3 ) _n --(wherein, _R3 represents an alkylene group having 1 to 10 carbon atoms, and m is an integer of 1 to 10 ) and the remainder represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]
or (c) a mixture of a phosphoric acid ester monomer represented by the above formula () and an amine compound represented by the above formula (): to the active energy ray-curable resin. On the other hand, 1~
_{40 %} by weight _{of the} following general formula _{( )} ; represents,
R ₁₁ represents an alkylene group having 2 to 6 carbon atoms, and q is an integer of 5 to 30. ), and the following general formula (); (In the formula, R ₄ represents a hydrogen atom or a methyl group,
R ₅ represents an alkylene group having 2 to 6 carbon atoms, R ₆ represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acryloyloxy group, or a methacryloyloxy group, and p is an integer of 13 to 30. . ) A coating agent for cationic dye dry transfer coloring, characterized in that it comprises at least one selected from the group consisting of polyoxyalkylene compounds represented by: 2. The coating agent according to claim 1, wherein the compound having cationic dye-dyeable dicite is a sulfonic acid group or a compound having a sulfonic acid group. 3. The coating agent according to claim 2, wherein the compound having a sulfonic acid group or a sulfonic acid group is a monomer having an acryloyl group or a methacryloyl group, or a copolymer containing the monomer. 4. The coating agent according to claim 2 or 3, wherein the sulfonic acid group is an ammonium sulfonate salt type group. 5 Claims in which the phosphate ester monomer is a monomer selected from the group consisting of acryloyloxyethyl phosphate, methacryloyloxyethyl phosphate, bis-acryloyloxyethyl phosphate, and bis-methacryloyloxyethyl phosphate Coating agent according to item 1. 6. The coating agent according to claim 1, wherein the amine compound is an alkyldiethanolamine having an alkyl group having 1 to 20 carbon atoms. 7. The active energy ray-curable resin is composed of at least one selected from the group consisting of monomers and oligomers, and the number of polymerizable groups or epoxy groups per molecule exceeds one on average. The coating agent according to claim 1. 8. The active energy ray-curable resin is composed of a mixture of a polymer and at least one selected from the group consisting of monomers and oligomers, and the number of polymerizable groups or epoxy groups is 1 on average per molecule. Claim 1 that exceeds
Coating agent described in section. 9 The active energy ray-curable resin is composed of a mixture of 0 to 30% by weight of a polymer and the remainder of at least one selected from the group consisting of monomers and oligomers, and 10% by weight or more of the oligomer has the general formula: [In the formula, N is an integer from 1 to 4, and at least 3 or more Xs are represented by the general formula: (In the formula, R ₇ represents a hydrogen atom or a methyl group,
R ₈ is a single bond, an alkylene group having 1 to 8 carbon atoms, or a polyoxyalkylene group having an alkylene group having 1 to 8 carbon atoms. ), the remainder is an alkyl group having 1 to 8 carbon atoms,
Hydroxyl group, amino group, group or formula represented by the formula: —(OR ₉ ) _M —H (wherein R ₉ represents an alkylene group having 1 to 8 carbon atoms, and M is a positive integer) :-(OR ₉ ) _M ---OH (in the formula, R ₉ and M are the same as above). ], and the number of polymerizable groups in the mixture is 1.5 on average per molecule.
The coating agent according to claim 1, wherein the coating agent is at least 100%. 10 An active energy ray-curable resin: (a) a compound having a cationic dye-dyeable dicite, or (b) a compound having a cationic dye-dyeable dicite, and a general formula; [In the formula, at least one X is a general formula; (In the formula, R ₁ represents a hydrogen atom or a methyl group,
_R2 represents an alkylene group having 1 to 10 carbon atoms, and n is an integer of 0 to 10. ), and the remainder represents a hydroxyl group. ] A phosphoric acid ester monomer represented by the general formula; [Wherein, at least one Y is a general formula; H-( _OR3 ) _n --(wherein, _R3 represents an alkylene group having 1 to 10 carbon atoms, and m is an integer of 1 to 10 ) and the remainder represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]
or (c) a mixture of a phosphoric acid ester monomer represented by the above formula () and an amine compound represented by the above formula (): to the active energy ray-curable resin. On the other hand, 1~
_{40 %} by weight _{of the} following general formula _{( )} ; represents,
R ₁₁ represents an alkylene group having 2 to 6 carbon atoms, and q is an integer of 5 to 30. ), and the following general formula (); (In the formula, R ₄ represents a hydrogen atom or a methyl group,
R ₅ represents an alkylene group having 2 to 6 carbon atoms,
R ₆ represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acryloyloxy group, or a methacryloyloxy group, and p is an integer of 13 to 30. ) A coating agent comprising at least one selected from the group consisting of polyoxyalkylene compounds represented by the following is applied to the surface of a film or paper, and then cured with active energy rays.An article for cationic dye dry transfer coloring. manufacturing method. 11. The manufacturing method according to claim 10, wherein the compound having cationic dye-dyeable dicite is a sulfonic acid group or a compound having a sulfonic acid group. 12. The production method according to claim 11, wherein the compound having a sulfonic acid group or a sulfonic acid group is a monomer having an acryloyl group or a methacryloyl group, or a copolymer containing the monomer. 13 Claim 11 or 1, wherein the sulfonic acid group is an ammonium sulfonic acid salt type group
The manufacturing method described in Section 2. 14 Claims in which the phosphate ester monomer is a monomer selected from the group consisting of acryloyloxyethyl phosphate, methacryloyloxyethyl phosphate, bis-acryloyloxyethyl phosphate, and bis-methacryloyloxyethyl phosphate The manufacturing method according to item 10. 15. The manufacturing method according to claim 10, wherein the amine compound is an alkyldiethanolamine having an alkyl group having 1 to 20 carbon atoms. 16 The active energy ray-curable resin is composed of at least one selected from the group consisting of monomers and oligomers, and the number of the polymerizable group or epoxy group is more than one per molecule on average. The manufacturing method according to claim 10. 17 The active energy ray-curable resin is composed of a mixture of a polymer and at least one selected from the group consisting of monomers and oligomers, and the number of polymerizable groups or epoxy groups is on average 1 per molecule. Claim 1 that exceeds
The manufacturing method described in item 0. 18 The active energy ray-curable resin is composed of a mixture of 0 to 30% by weight of a polymer and the remainder of at least one selected from the group consisting of monomers and oligomers, and 10% by weight or more of the oligomer has the general formula: [Wherein, N is an integer of 1 to 4, and at least 3 or more of X are general formulas; (In the formula, R ₇ represents a hydrogen atom or a methyl group,
R ₈ is a single bond, an alkylene group having 1 to 8 carbon atoms, or a polyoxyalkylene group having an alkylene group having 1 to 8 carbon atoms. ), the remainder is an alkyl group having 1 to 8 carbon atoms,
Hydroxyl group, amino group, group or formula represented by the formula: —(OR ₉ ) _M —H (wherein R ₉ represents an alkylene group having 1 to 8 carbon atoms, and M is a positive integer) :-(OR ₉ ) _M ---OH (in the formula, R ₉ and M are the same as above). ], and the number of polymerizable groups in the mixture is 1.5 on average per molecule.
11. The manufacturing method according to claim 10, wherein the manufacturing method is at least 100%. 19. The manufacturing method according to claim 10, wherein the film is a polyester film. 20. The manufacturing method according to claim 10, wherein the paper is acrylic paper mainly composed of acrylic fibers or art paper mainly composed of wood fibers. 21. The manufacturing method according to claim 10, wherein the active energy rays are ultraviolet rays with a wavelength of 100 to 800 nm.