JP2000212207A - Colored resin emulsion and colored microparticle transparent colored film, and transparent colored cured film prepared from the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colored resin emulsion excellent in durability by effecting the emulsion polymerization of a monomer composition and a dye composition containing an oil-soluble dye and an ultraviolet absorber and/or an ultraviolet stabilizer in the presence of a polymerization initiator and an emulsifier. SOLUTION: The monomer composition used is desirably the one containing at least 70 wt.% monomer of the formula (wherein R1 is H or methyl; and R2 is a 3-6C alkyl). The oil-soluble dye used is desirably the one having an organic solvent solubility (20 deg.C) of at least 1 wt.%, a water solubility (20 deg.C) of at most 1 wt.%, and a water solubility (100 deg.C) of at most 10 wt.%. The ultraviolet absorber and/or ultraviolet stabilizer used are desirably of a benzotriazole type, of a benzophenone type, or of a hindered amine type or are inorganic microparticles. The amount of the oil-soluble dye added is desirably 1-50 pts.wt. per 100 pts.wt. monomer composition. The amount of the ultraviolet absorber and/or ultraviolet stabilizer used is desirably 0.1-30 pts.wt. per 100 pts.wt. monomer composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored resin emulsion containing a high-concentration dye having excellent durability, and to colored fine particles, a transparent colored film and a transparent colored cured film using the same.

[0002]

2. Description of the Related Art Colored fine particles and emulsions in which colored fine particles are dispersed are used for various writing inks, printing inks, ink jet recording inks, paints, color filters, and the like, and the resulting printed matter is clear. Color needs to be maintained over a long period of time. For this reason, the colored fine particles are required to have high optical properties and high durability (heat resistance, light resistance, solvent resistance, water resistance, etc.) containing a coloring agent such as a dye in a high concentration.

[0003] One type of conventionally known method for producing colored fine particles is, for example, emulsion polymerization of vinyl chloride alone or a monomer copolymerizable with vinyl chloride and vinyl chloride, or suspension polymerization. A method for producing colored fine particles by producing polymer fine particles by using a dye and dyeing the same with a dye and a dyeing assistant is known. However, with such a method, it has been difficult to produce colored fine particles containing a dye at a high concentration having high optical properties and durability.

In Japanese Patent Publication No. 52-29336,
When one or more unsaturated monomers including butoxymethylacrylamide and the like are copolymerized with one or more unsaturated monomers including vinyl chloride and styrene, the above unsaturated A method is disclosed in which after dissolving or dispersing a dye in a monomer, the above unsaturated monomer is copolymerized to produce colored fine particles in which the inside is colored with a dye.

However, the colored fine particles obtained by this method do not contain a dye at a sufficiently high concentration and uniformly,
Further, it did not have sufficient optical characteristics and durability.

In ordinary inks and colored emulsions, it is difficult to realize a spectral spectrum of one primary color with one kind of dye, and usually, toning is performed by mixing several kinds of dyes. In this case, as the type of the dye, for example, a blue composition in which a phthalocyanine-based cyan dye and an anthraquinone-based cobalt dye are mixed, an azo metal complex-based yellow dye and a phthalocyanine-based cyan dye are mixed. There are green compositions and the like, but as can be seen from these examples, these materials are mixtures of dyes with completely different chemical structures. Therefore, when an emulsion containing these dye mixtures is to be prepared, the monomer composition used therein must be a good solvent that uniformly dissolves all the constituent dyes. In addition, if there is a considerable difference in solubility depending on the dye, a coating film formed from the mixture may have reduced light transmittance due to turbidity or a shift in spectral spectrum. Selection is important.

Further, since it is desirable that the colored fine particles have a high color density, it is required that not only the solubility in the dye is the same but also the solubility is high. That is, the first condition is to select a monomer composition that can be uniformly dissolved at a high concentration even with a mixture of dyes having completely different chemical structures. However, in the method for producing colored fine particles described in Japanese Patent Publication No. 52-29336, no consideration is given to them.

[0008] Colorants generally require durability. Generally, dyes are inferior in durability to pigments, but the durability is considerably improved depending on the resin material to be coated. The effect of the monomer structure is the largest to improve the durability, and crosslinking is also an effective means, but has the following problems. That is, the emulsion obtained by copolymerizing the polyfunctional monomer has a cross-linked structure, but when the concentration of the cross-linking agent is increased, the dispersion becomes unstable, and the film-forming property decreases,
There is a problem in that it is difficult to obtain a smooth and flexible film, and at present, a sufficiently satisfactory colored resin emulsion has not been obtained.

[0009]

DISCLOSURE OF THE INVENTION In view of the above, the present invention provides a monomer composition having a heat-condensable side chain in which a mixture of dyes having completely different chemical structures is uniformly and highly mixed. It is an object of the present invention to provide a colored resin emulsion having excellent durability, especially light resistance, and a colored fine particle, a transparent colored film, and a transparent colored cured film using the same.

[0010]

According to the present invention, a dye composition comprising an oil-soluble dye and a UV absorber and / or a UV stabilizer in a monomer composition is emulsified in the presence of a polymerization initiator and an emulsifier. It is a colored resin emulsion obtained by polymerization. Hereinafter, the present invention will be described in detail.

The above-mentioned monomer composition is not particularly limited. For example, the following general formula (I):

[0012]

Embedded image Those containing 70% by weight or more of the monomer represented by the following formula (hereinafter also referred to as polymerizable monomer (I)) are suitably used. In the above monomer composition, R ¹ represents a hydrogen atom or a methyl group. Therefore, the monomer composition is an acrylamide derivative or a methacrylamide derivative. R ² represents an alkyl group having 3 to 7 carbon atoms. As R ² , for example, n-propyl group, i-propyl group, n
-Butyl group, i-butyl group, t-butyl group and the like. If the content of the polymerizable monomer (I) is less than 70% by weight, it may be difficult to dissolve the dye at a high concentration, so the above range is preferable. The monomer composition,
The polymerizable monomer (I) alone may be used, or a mixture with another polymerizable monomer may be used.

The other polymerizable monomer is not particularly limited as long as it is copolymerizable with the polymerizable monomer (I) and is capable of dissolving the dye. Glycidyl methacrylate, methyl methacrylate,
Polymerizable monomers having one polymerizable unsaturated bond in one molecule such as ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, styrene, methacrylamide, etc .; ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, Polymerizable monomer having two or more polymerizable unsaturated bonds in one molecule such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, allyl methacrylate, vinyl methacrylate, glycerol dimethacrylate, divinylbenzene, triallyl isocyanurate, etc. Body and the like. Among these, glycidyl methacrylate is preferred because of its excellent solubility in a wide range of oil-soluble dyes. The other polymerizable monomers may be used alone or in combination of two or more.

The compounding amount of the other polymerizable monomer is preferably not more than 30% by weight of the total monomer, but the other polymerizable monomer is one polymerizable in one molecule. In the case of a polymerizable monomer having an unsaturated bond, the content is preferably 10% by weight or less, more preferably 5% by weight or less. When the other polymerizable monomer is a polymerizable monomer having two or more polymerizable unsaturated bonds in one molecule, the content is preferably 0.1 to 10% by weight, and more preferably 0.5 to 10% by weight. 5% by weight is more preferred. When the amount of the polymerizable monomer having two or more polymerizable unsaturated bonds in one molecule is less than 0.1% by weight, the polymerization rate is accelerated, and the effect of fixing the dye in the emulsion particles can not be expected much. When the content exceeds 10% by weight, not only the solubility of the dye is lowered, but also the aggregation of emulsion particles and the precipitation of the dye are liable to occur.

The oil-soluble dye has a solubility in an organic solvent at 20 ° C. of 1% by weight or more. Examples of the organic solvent include, but are not particularly limited to, hydrocarbons, halogenated hydrocarbons, ketones, esters, alcohols, and amides. Preferably, it has a solubility in the above organic solvent, a solubility in water at 20 ° C. of 1% by weight or less, and a solubility in water at 100 ° C. of 10% by weight or less.

Oil-soluble dyes having a solubility in an organic solvent at 20 ° C. of 1% by weight or more, a solubility in water at 20 ° C. of 1% by weight or less, and a solubility in water at 100 ° C. of 10% by weight or less include For example, azo dyes, anthraquinone dyes, phthalocyanine dyes, triphenylmethane dyes and the like; azo metal complex dyes, salts of anionic dyes and cationic monomers, salts of anionic dyes and cationic dyes ; Color index number so
lvent blue 44, 45, 59, 104; so
lvent red 24, 68, 89, 124; sol
vent yellow13, 14, 33, 79, 9
3; bat blue 1 and 6; bat yellow 6
And the like.

The cationic monomer is not particularly limited as long as it reacts with the anionic dye to form a salt. However, since it has high compatibility with the polymerizable monomer (I), General formula (II);

[0018]

Embedded image

(Wherein, R ³ represents a hydrogen atom or a methyl group, and R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 8 carbon atoms, an aralkyl group or a cycloalkyl group) X represents a halogen atom, and R ⁴ , R ⁵ , R
The total number of carbon atoms contained in the group represented by ⁶ is 8 or more).

In the above cationic monomer, R ³ is
Represents a hydrogen atom or a methyl group. Therefore, the monomer composition is an acrylamide derivative or a methacrylamide derivative. R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 8 carbon atoms, an aralkyl group or a cycloalkyl group. Examples of R ⁴ , R ⁵ , and R ⁶ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a benzyl group, and a cyclohexyl group.

The total number of carbon atoms contained in the groups represented by R ⁴ , R ⁵ and R ⁶ is 8 or more. Examples of the combination thereof include a methyl group, a methyl group and a benzyl group, an ethyl group, Examples include an ethyl group and a benzyl group.

When the total number of carbon atoms contained in the groups represented by R ⁴ , R ⁵ and R ⁶ is less than 8, the hydrophilicity is so strong that a hydrophobic salt is formed by the reaction with the anionic dye. It is not preferable because it is difficult. The cationic monomer represented by the general formula (II) has relatively strong hydrophobicity, and can precipitate a salt by reacting with the anionic dye.

Further, the cationic monomer represented by the above general formula (II) and the above monomer composition are copolymerized to fix the oil-soluble dye on the resulting polymer. Desorption of the oil-soluble dye can be suppressed. The amount of the dye is preferably 1 to 50 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the monomer composition.
30 parts by weight. When the amount is more than 50 parts by weight, the concentration of the dye composition becomes too high, which makes it difficult to add the dye composition and also separates the dye during polymerization.

When a salt obtained by reacting the anionic dye with a cationic monomer is used as the oil-soluble dye, the monomer composition for dissolving the oil-soluble dye may be the polymerizable compound described above. 90% by weight of monomer (I)
It is more preferable to use a monomer composition containing the above.

The dye composition used in the colored resin emulsion of the present invention contains an ultraviolet absorber and / or an ultraviolet stabilizer. The ultraviolet absorber and / or ultraviolet stabilizer is not particularly limited, and includes, for example, an organic ultraviolet absorber or ultraviolet stabilizer composed of benzotriazole, benzophenone, or hindered amine, and inorganic fine particles. It is preferable that at least one member selected from the group is used.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole. And a polymer of 2- (2′-hydroxy-5′-methacryloxyphenyl) -2H-benzotriazole (trade name “PUVA-93” manufactured by Otsuka Chemical Co., Ltd.).
As the benzophenone-based ultraviolet absorber, for example,
2,4-hydroxybenzophenone, 2-hydroxy-
4-methoxybenzophenone and the like. The hindered amine-based ultraviolet stabilizer is not particularly limited. For example, ADK STAB LA-77 (manufactured by Asahi Denka Co., Ltd.), Tinuvin 622LD, Tinuvin 144 (manufactured by Ciba Geigy), Sanol LS-2626 (manufactured by Sankyo) ) And the like.

As the ultraviolet absorber, inorganic fine particles can also be suitably used. Examples of the inorganic fine particles include titanium oxide and cerium oxide. These UV absorbers and UV stabilizers may be used alone or in combination of two or more. The amount of the ultraviolet absorber and the ultraviolet stabilizer is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the monomer composition.

The above-mentioned ultraviolet absorber and ultraviolet stabilizer are organic ultraviolet absorbers or ultraviolet stabilizers of benzotriazole, benzophenone or hindered amine type having a polymerizable group in the molecule copolymerizable with the monomer composition. May be selected from the group of. Examples of the polymerizable group include a vinyl group, an acryl group, and a methacryl group. Examples of the organic ultraviolet absorber and the ultraviolet stabilizer having the polymerizable group in the molecule include, for example, 2- (2 ′
-Hydroxy-5'-methacryloxyphenyl) -2H
-Benzotriazole (trade name “PUV manufactured by Otsuka Chemical Co., Ltd.
A-93 "), ADK STAB LA-82 and LA-87
(All manufactured by Asahi Denka Co., Ltd., trade name) and the like.

Since these organic ultraviolet absorbers and ultraviolet stabilizers are incorporated into the molecular chains at the time of polymerization of the monomer composition, there is no danger of volatilization or bleed-out, and a stable light resistance can be imparted for a long period of time. What you get. The compounding amount of the organic ultraviolet absorber and the ultraviolet stabilizer having the polymerizable group in the molecule is 0.1 to 100 parts by weight of the monomer composition.
The amount is preferably 1 to 30 parts by weight, more preferably 0.5 to 1 part.
0 parts by weight.

The colored resin emulsion of the present invention is obtained by dispersing the above dye composition in the presence of a polymerization initiator and an emulsifier, followed by emulsion polymerization. The polymerization initiator is not particularly limited, and includes, for example, an oil-soluble or water-soluble organic azo compound, an inorganic peroxide such as potassium persulfate, ammonium persulfate, an organic peroxide, the inorganic peroxide and a sulfite, and the like. Redox compositions in combination with the above reducing agents. Among them, organic azo compounds are preferable, and the decomposition temperature is 40 to 80 with a half life of 10 hours.
Organic azo compounds at ℃ are more preferred.

The water-soluble organic azo compound includes a cationic compound and an anionic compound. Among these, which organic azo compound is used is not particularly limited, and an optimum one may be used according to an emulsifier described later.

When a metal complex of the above-mentioned azo dye and / or a salt obtained by reacting the above-mentioned anionic dye with a cationic monomer is used as the above-mentioned oil-soluble dye, an oil is used as a polymerization initiator. It is preferable to use a soluble organic azo compound.

The emulsifier is not particularly limited, and for example, anionic, cationic and nonionic surfactants can be used. Among these, anionic surfactants are preferred because cationic surfactants do not have strong dispersibility and nonionic surfactants tend to increase the particle size of the resulting emulsion. When an anionic surfactant is used as the emulsifier, it is preferable to use an anionic organic azo compound as the polymerization initiator because of little interaction with the emulsifier.

Examples of the anionic surfactant include alkyl sulfates such as sodium alkyl sulfate and ammonium alkyl sulfate, and alkyl sulfonates such as sodium alkyl sulfonate and ammonium alkyl sulfonate. Among these, alkyl sulfonates are more preferred because phosphate esters having a polymerizable unsaturated bond are fixed to the emulsion particles and thus have the advantage of not adversely affecting the physical properties of the coating film.

The method for producing the colored resin emulsion by the emulsion polymerization is not particularly limited, and the reaction conditions may be set according to the type of the dye-containing composition, the polymerization initiator, and the emulsifier used. For example, a monomer composition containing the polymerizable monomer (I), an emulsifier, and deionized water are charged into a flask, and the temperature is raised to a reaction temperature while stirring under a nitrogen stream, and then A polymerization initiator solution was poured into the flask, and a dye solution containing an oil-soluble dye was added to the flask.
A colored resin emulsion can be produced by dropping over 2 to 2 hours, further stirring at the same temperature for 3 to 4 hours, and then performing emulsion polymerization using a method such as cooling to room temperature.

The amount of the polymerization initiator is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the monomer composition.
More preferably, it is 0.2 to 5 parts by weight. The concentration of the emulsifier is not particularly limited, but is preferably 0.5 to 10% by weight. The amount of the emulsifier is not particularly limited, but is preferably 1/5 to 1/1 by weight of the dye composition to the aqueous emulsifier solution. The reaction temperature is not particularly limited, but is usually preferably 10 to 100 ° C. More preferably, it is 40 to 80 ° C.

The obtained colored resin emulsion has high optical properties and high durability in which fine particles containing a dye in a high concentration are dispersed. In particular, when using a salt obtained by reacting an anionic dye and a cationic monomer as an oil-soluble dye, since the cationic monomer is incorporated into the copolymer, the anionic dye is It is firmly fixed in the copolymerized fine particles by ionic bonding.

The salt obtained by reacting the above-mentioned anionic dye with a cationic monomer does not dissolve in most hydrophobic monomers, but dissolves in the polymerizable monomer (I). Then, by combining with an oil-soluble organic azo compound as a polymerization initiator, the polymerization reaction proceeds, and a colored resin emulsion having the above characteristics is obtained.

When a metal complex of the azo dye is used as the oil-soluble dye, the polymerization reaction proceeds by using an oil-soluble organic azo compound as a polymerization initiator, and the dye is contained at a high concentration. A colored resin emulsion having high optical properties and durability in which fine particles are dispersed can be obtained.

Further, by further adding a water-dispersible ultraviolet absorber to the colored resin emulsion obtained by the emulsion polymerization, higher light resistance can be imparted. Examples of the water-dispersible ultraviolet absorber include ADK STAB LX-301 and LX-332 (all manufactured by Asahi Denka Co., Ltd.), Needal W-10 and U-15 (all manufactured by Taki Chemical Co., Ltd.) and the like. Can be

If the content of the water-dispersible ultraviolet absorber is too small, no effect will be exhibited, and if it is too large, the strength of the obtained film or the like may decrease or the transparency of the film or the like may deteriorate. The water-dispersible ultraviolet absorber is preferably about 0.5 to 30 parts by weight based on 100 parts by weight of the solid content of the colored resin emulsion.

After the solvent in the obtained colored resin emulsion is dispersed, washing and the like are performed to obtain colored fine particles.

Casting a colored resin emulsion obtained by the emulsion polymerization, a mixed solution of the colored resin emulsion and a resin emulsion containing no dye, or a mixed solution of the colored resin emulsion and an aqueous resin solution on a substrate; Thereby, it is possible to form a uniform and flexible transparent colored film that does not include cracks.

The method of casting on the substrate is not particularly limited as long as the method can uniformly cast the colored resin emulsion or the mixed solution on the substrate. Examples include a method used for ordinary printing such as a coating method and a screen printing method. The transparent colored film is also one of the present invention.

By subjecting the transparent colored film to a heat treatment, a transparent colored cured film can be suitably formed.
The transparent colored cured film is a uniform and transparent continuous film containing no cracks, and is not dissolved in an organic solvent, so that it can be used for coloring various substrates. The transparent colored cured film is also one of the present invention.

[0046]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 2 parts by weight of sodium dodecyl sulfate, 4 parts by weight of New Frontier S510 (trade name, polymerizable surfactant having a phosphate group, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 194 parts by weight of deionized water And 10 parts by weight of n-butoxymethylacrylamide were charged into a flask, and the liquid temperature was raised to 50 ° C. while stirring under a nitrogen stream. Next, 10 parts by weight of an ethanol solution containing 0.5 parts by weight of V-70 (trade name, oil-soluble azo polymerization initiator, manufactured by Wako Pure Chemical Industries, Ltd.) was injected into the flask, and immediately n-butoxymethylacrylamide was added. 89 parts by weight, 1 part by weight of ethylene glycol dimethacrylate, 25 parts by weight of Savinyl PINK6BLS (manufactured by Clariant, trade name, magenta-based oil-soluble dye), and Tinuvin 326 (manufactured by Ciba Geigy, trade name;
A dye solution having a composition consisting of 5 parts by weight of a triazole-based ultraviolet absorber was started to be dropped, and the dropping was completed 2 hours later.

After stirring at the same temperature for 3 hours, the mixture was cooled to room temperature to obtain a colored resin emulsion. The obtained colored resin emulsion was filtered through a filter having a pore size of 1 μm, and then the particle size of the thermosetting colored resin was measured using a laser light scattering type particle size distribution analyzer (manufactured by Otsuka Electronics Co., Ltd.). The diameter was 92 nm.

Further, the obtained colored resin emulsion was cast on a glass plate, heat-treated at 150 ° C. for 10 minutes, and immersed in cyclohexane, but no elution of the dye was observed even after one week at room temperature. .

(Example 2) Instead of tinuvin 326, R
A colored resin emulsion was obtained in the same manner as in Example 1 except that 5 parts by weight of UVA-93 (trade name, manufactured by Otsuka Chemical Co., Ltd., triazole-based polymerizable ultraviolet absorber) was used. The obtained colored resin emulsion was cast on a glass plate as in Example 1, heat-treated at 150 ° C. for 10 minutes, and then immersed in cyclohexane, but no elution of the dye was observed even after one week at room temperature. Was.

(Example 3) 100 parts by weight of the colored resin emulsion of Example 1 was mixed with 10 parts by weight of a water-dispersible ultraviolet absorber (trade name "ADK STAB LX-301" manufactured by Asahi Denka Co., Ltd.) to give a colored resin. An emulsion was obtained. The obtained colored resin emulsion was cast on a glass plate as in Example 1, heat-treated at 150 ° C. for 10 minutes, and then immersed in cyclohexane, but no elution of the dye was observed even after one week at room temperature. Was.

Comparative Example 1 A colored resin emulsion was prepared in the same manner as in Example 1 except that tinuvin 326 was not used. The obtained colored resin emulsion was cast on a glass plate as in Example 1, heat-treated at 150 ° C. for 10 minutes, and then immersed in cyclohexane, but no elution of the dye was observed even after one week at room temperature. Was.

Comparative Example 2 Subvinyl PINK6BLS
(Clariant, trade name, magenta oil-soluble dye) was dissolved in acetone, cast on a glass plate in the same manner as in Example 1, and heat-treated at 150 ° C. for 10 minutes to form a coating film.

The light resistance of the obtained transparent colored cured film was measured using a fade meter (manufactured by Heraeus, “Santest cp”).
s "), the color difference ΔE after irradiation for 48 hours was measured, and the light resistance was evaluated. The evaluation results are shown in Table 1.

[0055]

[Table 1]

[0056]

As described above, the colored resin emulsion of the present invention comprises a mixture of dyes having completely different chemical structures in a uniform and high concentration, and a monomer having a heat-condensable side chain. Since it is composed of a composition, it has high optical properties and durability, and the colored fine particles, transparent colored film, and transparent colored cured film using the same also have high optical properties and durability.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4F071 AA22X AA31X AA33X AA35 AA35X AA51X AB18 AB24 AC07 AC08 AC12 AC14 AC15 AE05 AE06 AE09 BA04 BB02 BC01 4J011 AA05 KA04 KA05 KA07 KB22 KB29 PA27 PA38 PC39 PA27 PA38 PC02 PA27 AB16T AL03S AL08R AL09S AL11S AL62S AL63S AL66S AL75T AM15S AM21P AM21Q AQ21T BA03R BA03S BA04P BA08S BA11S BA32Q BC43R BC73R BC73S CA04 CA05 CA06 DA36 EA05 EA07 FA03 FA20 JA01 JA07 JA32

Claims (12)

[Claims] 1. A dye composition comprising an oil-soluble dye and an ultraviolet absorber and / or an ultraviolet stabilizer in a monomer composition, which is obtained by emulsion polymerization in the presence of a polymerization initiator and an emulsifier. Characterized colored resin emulsion. 2. The oil-soluble dye has a solubility in an organic solvent at 20 ° C. of 1% by weight or more, a solubility in water at 20 ° C. of 1% by weight or less, and a solubility in water at 100 ° C. of 1% by weight.
The colored resin emulsion according to claim 1, wherein the content is 0% by weight or less. 3. The method according to claim 1, wherein the monomer composition is represented by the general formula (I): (Wherein, R ¹ represents a hydrogen atom or a methyl group;
² represents an alkyl group having 3 to 6 carbon atoms. 3. The colored resin emulsion according to claim 1, which contains at least 70% by weight of the monomer represented by the formula (1). 4. An oil-soluble dye comprising an anionic dye and a compound represented by the general formula (II): (Wherein, R ³ represents a hydrogen atom or a methyl group, R ^4,
R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 8 carbon atoms, an aralkyl group or a cycloalkyl group;
Represents a halogen atom, and the total number of carbon atoms contained in the groups represented by R ⁴ , R ⁵ and R ⁶ is 8 or more. 4. The colored resin emulsion according to claim 1, which is a salt obtained by reacting a cationic monomer represented by the formula (1). 5. The colored resin emulsion according to claim 1, wherein the oil-soluble dye is a metal complex of an azo dye. 6. The ultraviolet absorber and / or ultraviolet stabilizer is at least one selected from the group consisting of an organic ultraviolet absorber or ultraviolet stabilizer comprising a benzotriazole, benzophenone, or hindered amine, and inorganic fine particles. The colored resin emulsion according to claim 1, wherein: 7. An organic ultraviolet absorber comprising a benzotriazole-based, benzophenone-based, or hindered amine-based ultraviolet absorber and / or ultraviolet stabilizer having a polymerizable group in a molecule capable of copolymerizing with the monomer composition. The colored resin emulsion according to claim 1, wherein the emulsion is at least one member selected from the group consisting of ultraviolet stabilizers. 8. The colored resin emulsion according to claim 1, wherein the polymerization initiator is an oil-soluble azo compound. 9. The colored resin emulsion according to claim 1, wherein a water-dispersible ultraviolet absorber is further added to the colored resin emulsion according to claim 1. 10. Colored fine particles obtained from the colored resin emulsion according to claim 1. Description: 11. The colored resin emulsion according to claim 1, a mixed liquid of the colored resin emulsion and a resin emulsion containing no dye, or a mixed liquid of the colored resin emulsion and an aqueous resin solution is flowed on a substrate. A transparent colored film formed by extending. 12. A transparent colored cured film formed by subjecting the transparent colored film according to claim 11 to heat treatment.