JP2001181528A - Fine coloring particle, colored resin emulsion, and ink for ink jet printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide fine coloring particles excellent in durability, especially light resistance, and prepared by homogeneously compounding a mixture of dyes having entirely different structures in a high concentration and to provide a colored resin emulsion and an ink for ink jet printing. SOLUTION: The fine coloring particle comprises a shell layer containing an ultraviolet absorber or an ultraviolet reflector and a core comprising an oil-soluble dye and a polymer which is prepared by polymerizing a monomer composition containing at least 30 wt.% monomer represented by formula I, wherein R1 is H or methyl; and R2 is a 3-6C alkyl.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to colored fine particles, a colored resin emulsion and an ink for ink jet printing which contain a high concentration of a dye and have excellent durability.

[0002]

2. Description of the Related Art Colored fine particles and emulsions in which the colored fine particles are dispersed are used for various writing inks, printing inks, ink jet recording inks, paints, color filters and the like. Since the obtained printed matter is required to maintain a clear color for a long period of time, the colored fine particles contain a coloring agent such as a dye at a high concentration, and have optical properties and durability (heat resistance, light resistance, Solvent, water resistance, etc.)
Needs to be high.

[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 and having high optical properties and durability.

Japanese Patent Publication No. 52-29336 discloses one or more unsaturated monomers containing butoxymethylacrylamide and one unsaturated monomer containing vinyl chloride, styrene and the like. Or when performing copolymerization with two or more, after dissolving or dispersing the dye in the unsaturated monomer,
A method is disclosed in which the unsaturated monomer is copolymerized to produce colored fine particles in which the interior 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, and do not have sufficient optical properties 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. Green compositions and the like can be mentioned. As can be seen from these examples, these materials are mixtures of dyes having completely different chemical structures. Therefore, when preparing an emulsion containing a mixture of these dyes, the monomer composition used therein must be a good solvent that can uniformly and highly dissolve all the constituent dyes.

[0006] When there is a considerable difference in solubility between dyes, a coating film formed from the mixture may be turbid, resulting in a decrease in light transmittance or a shift in spectral spectrum. The choice of the monomer is important. As described above, it is necessary to select a monomer composition as a raw material of the colored fine particles that can be uniformly dissolved at a high concentration even with a mixture of dyes having completely different structures.
JP-A-29336 does not take such measures into consideration.

[0007] Colorants generally require durability. Dyes are inferior in durability to pigments, but are said to have considerably improved durability depending on the resin material to be coated. The effect of the monomer structure to be dissolved has the greatest effect on improving 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 that it is difficult to obtain a smooth and flexible film. Therefore, a sufficiently satisfactory colored resin emulsion has not been obtained.

[0008]

DISCLOSURE OF THE INVENTION In view of the above, the present invention is directed to a coloring method in which a mixture of dyes having excellent durability and, in particular, light resistance and having completely different chemical structures is uniformly and highly concentrated. It is an object to provide fine particles, a colored resin emulsion, and an ink for inkjet printing.

[0009]

The present invention provides a compound represented by the following general formula (I):

[0010]

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(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 3 to 6 carbon atoms). Colored fine particles comprising a core made of a polymer and an oil-soluble dye using the body composition as a polymerization raw material, and a shell layer containing an ultraviolet absorber or an ultraviolet reflector. Hereinafter, the present invention will be described in detail.

The colored fine particles of the present invention comprise a core and a shell layer. The above-mentioned core part consists of a polymer which uses a monomer composition containing at least 30% by weight of the monomer represented by the above general formula (I) as a polymerization raw material, and an oil-soluble dye.

In the monomer represented by the above general formula (I) (hereinafter referred to as polymerizable monomer (I)), R ¹ represents a hydrogen atom or a methyl group. Therefore, the polymerizable monomer (I) is an acrylamide derivative or a methacrylamide derivative. In the above polymerizable monomer (I), R
² represents an alkyl group having 3 to 6 carbon atoms. Examples of R ² include an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, and the like.

The monomer composition contains at least 30% by weight of the polymerizable monomer (I). That is, the monomer composition is obtained by mixing the polymerizable monomer (I) with 30 to 100.
% By weight, but the content of the polymerizable monomer (I) is 30%.
If the amount is less than% by weight, it is difficult to dissolve the dye at a high concentration. The monomer composition may consist of the polymerizable monomer (I) alone or may be a mixture with another polymerizable monomer.

The other polymerizable monomer is not particularly limited as long as it is copolymerizable with the polymerizable monomer (I) and can dissolve the oil-soluble dye. For example, a polymerizable monomer having one polymerizable unsaturated bond in one molecule such as glycidyl methacrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, styrene, methacrylamide and the like. Monomer: ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, allyl methacrylate, vinyl methacrylate, glycerol dimethacrylate, divinylbenzene, triallyl isocyanurate Polymerizable monomers and the like having two or more polymerizable unsaturated bonds in a molecule thereof. 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 amount of the other polymerizable monomer is preferably not more than 70% by weight of the total monomer composition. When the other polymerizable monomer is a polymerizable monomer having one polymerizable unsaturated bond in one molecule, the content is more preferably 30% by weight or less. When the other polymerizable monomer is a polymerizable monomer having two or more polymerizable unsaturated bonds in one molecule, 0.1
-10% 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 colored fine particles is not expected much. When the content is more than 10% by weight, not only the solubility of the dye is reduced, but also the aggregation of the colored fine particles and the precipitation of the dye are liable to occur, so that the above range is more preferable. More preferably, it is 0.5 to 5% by weight.

The oil-soluble dye is not particularly limited, but preferably has a solubility in an organic solvent at 20 ° C. of 1% by weight or more. The organic solvent is not particularly restricted but includes, for example, hydrocarbons, halogenated hydrocarbons, ketones, esters, alcohols, amides and the like. The oil-soluble dye has a solubility in the 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. Are more preferred.

An oil 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. Examples of the soluble dye include an azo dye, an anthraquinone dye, a phthalocyanine dye, a triphenylmethane dye, an azo metal complex dye, and the like.
nt blue 44, 45, 59, 104; solvent
nt red 24, 68, 89, 124; solvent
t yellow 13, 14, 33, 79, 93; va
t blue 1, 6; bat yellow 6 and the like.

An oil 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. Examples of the soluble dye include a salt obtained by reacting an anionic dye and a cationic monomer, and a salt obtained by reacting an anionic dye and a cationic dye. The cationic monomer is not particularly limited as long as it reacts with an anionic dye to form a salt, and the polymerizable monomer (I)
Having high compatibility with the following general formula (II):

[0020]

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(Where R^Three Represents a hydrogen atom or a methyl group
Represents, R^Four , R^Five , R⁶ Are the same or different,
An alkyl group having 1 to 8, an aralkyl group having 1 to 8 carbon atoms, or
X represents a cycloalkyl group having 4 to 8 carbon atoms;
Represents an atom^Four , R^Five , R ⁶ Included in the group represented by
The total number of carbon atoms is 8 or more)
Monomers are preferred.

In the cationic monomer represented by the general formula (II), R ³ represents a hydrogen atom or a methyl group. Therefore, the cationic monomer represented by the general formula (II) is an acrylamide derivative or a methacrylamide derivative. R ⁴ , R ⁵ and R ⁶ are the same or different and represent an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 4 to 8 carbon atoms. R
^4, the R ^5, R ^6, for example, a methyl group, an ethyl group, n- propyl group, i- propyl group, a benzyl group, a cyclohexyl group and the like.

The above R^Four , R^Five , R⁶ Included in the group represented by
The total number of carbon atoms is 8 or more,^Four , R^Five , R
⁶ Are, for example, R^Four As methyl
Group, R ^Five Represents a methyl group or a benzyl group, R⁶ As
Is an ethyl group, an ethyl group or 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 cationic monomer is
Strongly hydrophilic, it is difficult to form a hydrophobic salt by reaction with the anionic dye. 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 general formula (II) and the monomer composition are copolymerized, whereby the oil-soluble dye is fixed on the resulting polymer, and the oil-soluble dye is fixed. Desorption of the dye can be suppressed. The amount of the oil-soluble dye is 1 to 100 parts by weight of the monomer composition.
~ 50 parts by weight are preferred. If the amount exceeds 50 parts by weight, the concentration of the mixture of the cationic monomer represented by the general formula (II) and the monomer composition becomes too high, which not only makes it difficult to add, but also causes Since the oil-soluble dye may separate, the above range is preferable. More preferably 5
-30 parts by weight.

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

The shell layer contains an ultraviolet absorber or an ultraviolet reflector. Examples of the ultraviolet absorber include an inorganic ultraviolet absorber and an organic ultraviolet absorber. Examples of the inorganic ultraviolet absorber include metal oxides such as titanium oxide, cerium oxide, and zinc oxide. The metal oxide also functions as an ultraviolet reflector.

When the above-mentioned inorganic ultraviolet absorber is used, the method for forming the above-mentioned shell layer is as follows.
And a vapor phase method such as a vapor deposition method, an ion plating method, and a sputtering method.

When the colored fine particles of the present invention are dispersed in an aqueous solvent, the shell layer can be formed by a sol-gel method (alkoxide method), a plating method, or a method of forming a metal oxide colloid onto the surface of the core. And the like.

As a method for forming the shell layer by the sol-gel method (alkoxide method), for example, a metal alkoxide such as titanium, cerium, or zinc is dissolved in a monomer having a polymerizable group, and the metal alkoxide is formed. Is added directly to the emulsion of the core after the polymerization of the core, or a solution obtained by emulsifying a monomer in which a metal alkoxide is dissolved by adding a surfactant to the core is used. By adding to the emulsion and polymerizing, a resin layer containing a metal alkoxide is formed on the surface of the core portion, and then an alkali such as sodium hydroxide solution is added to hydrolyze the metal alkoxide to form a metal. A method of transforming into an oxide is exemplified. As the monomer having a polymerizable group, for example, the polymerizable monomer (I) and other polymerizable monomers can be used. When the above-mentioned inorganic ultraviolet absorber is used, the shell layer is made of 30 inorganic ultraviolet absorbers.
It is preferred that the content be at least 10 wt%.

Examples of the organic ultraviolet absorber include a benzotriazole ultraviolet absorber and a benzophenone ultraviolet absorber. Examples of the benzotriazole-based ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, (2′-hydroxy-
3 ', 5'-di-t-butylphenyl) benzotriazole and the like. Examples of the benzophenone-based ultraviolet absorber include 2,4-hydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone.

The organic UV absorber incorporated in the copolymer includes, for example, poly (2-
(2'-hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole) (trade name PUVA-
93, manufactured by Otsuka Chemical Co., Ltd.).

When a hindered amine-based ultraviolet absorber is used in combination with the above-mentioned organic ultraviolet absorber, the light resistance of the colored fine particles of the present invention is further improved. As the hindered amine ultraviolet stabilizer, for example, ADK STAB LA-77
(Made by Asahi Denka), Tinuvin 622LD, Tinuvin 144
(Manufactured by Ciba-Geigy), Sanol LS-2626 (manufactured by Sankyo) and the like.

When the above-mentioned organic ultraviolet absorbent is used, the shell layer may be formed, for example, by adding a monomer in which the organic ultraviolet absorbent is dissolved in the same manner as in the case of using the above-mentioned inorganic ultraviolet absorbent. Polymerization on the surface of the part. When the above-mentioned organic ultraviolet absorber is used, the shell layer preferably contains the organic ultraviolet absorber in an amount of 30% by weight or more.

The inorganic ultraviolet absorber and the organic ultraviolet absorber may be used in combination. Another ultraviolet absorber may be used in combination with the ultraviolet absorber and the ultraviolet stabilizer. As the other ultraviolet absorber, for example, those selected from benzotriazole-based, benzophenone-based, and hindered amine-based and having a polymerizable group in the molecule can be used. Examples of the polymerizable group include a vinyl group, an acryl group, and a methacryl group.

Examples of the other ultraviolet absorbent include, for example,
2- (2'-hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole (trade name: RUVA-
93, manufactured by Otsuka Chemical Co., Ltd.) and ADK STAB LA-82, LA
-87 (manufactured by Asahi Denka Co., Ltd.). The shell layer preferably contains the other ultraviolet absorber in an amount of 30% by weight or more.

In the colored fine particles of the present invention, since these ultraviolet absorbers or ultraviolet reflectors are incorporated into the molecular chains at the time of polymerization, there is no fear of volatilization and stable light resistance can be obtained.

The above-mentioned monomer composition and oil-soluble dye are dispersed in the presence of a polymerization initiator and an emulsifier, and then emulsion polymerization is carried out to form a colored resin obtained by dispersing the colored fine particles of the present invention in an aqueous solvent. An emulsion can be obtained.
The colored resin emulsion is also one of the present invention.

The polymerization initiator is not particularly limited.
For example, oil-soluble or water-soluble organic azo compounds, potassium persulfate, inorganic peroxides such as ammonium persulfate, organic peroxides, redox compositions and the like in combination of reducing agents such as inorganic peroxides and sulfites. Can be Among these, an organic azo compound is preferable, and an organic azo compound having a half-life of 10 hours and a decomposition temperature of 40 to 80 ° C is more preferable.

The water-soluble organic azo compound includes a cationic compound and an anionic compound.
Which organic azo compound to use is not particularly limited,
An optimum one may be used according to the emulsifier described below.

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

The emulsifier is not particularly limited, and for example, an anionic surfactant, a cationic surfactant, and a nonionic surfactant 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 above 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. Of these, alkyl sulfonates are preferred because the phosphate having a polymerizable unsaturated bond is fixed to the emulsion particles and has the advantage of not adversely affecting the physical properties of the coating film.

The method for producing the colored resin emulsion of the present invention by the above emulsion polymerization is not particularly limited, and the reaction conditions are 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 the reaction temperature while stirring under a nitrogen stream. Then, a solution of the polymerization initiator is poured into the flask, a dye solution containing an oil-soluble dye is dropped over 1 to 2 hours, and further stirred at the same temperature for 3 to 4 hours, and then cooled to room temperature. By performing emulsion polymerization using the above method, a colored resin emulsion can be produced.

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,
The weight ratio of the dye composition to the aqueous emulsifier solution is 1/5 to 1
/ 1 is preferred. The reaction temperature is not particularly limited,
Usually, 10 to 100 ° C. is preferable. More preferably, 4
0-80 ° C.

The colored resin emulsion of the present invention thus obtained has the optical particles and the colored fine particles of the present invention dispersed in a high concentration, and has high optical properties and durability. In particular, when a salt obtained by reacting an anionic dye and a cationic monomer is used as an oil-soluble dye, the cationic monomer is incorporated into the polymer, so that the anionic dye is ion-bonded. And is firmly fixed in the colored fine particles via the polymer.

The salt obtained by reacting an anionic dye with a cationic monomer does not dissolve in most hydrophobic monomers, but dissolves in the polymerizable monomer (I). 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-mentioned properties is obtained.

When a metal complex of an 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.
A colored resin emulsion having high optical properties and durability in which fine particles containing a dye in a high concentration are dispersed can be obtained. After the solvent in the obtained colored resin emulsion of the present invention is dispersed, washing and the like are performed to obtain the colored fine particles of the present invention.

The colored fine particles of the present invention have an average particle size of 200
nm or less. Average particle size is 200nm
If the ratio exceeds, problems such as precipitation of colored fine particles in the colored resin emulsion and clouding after printing will occur. Preferably it is 10 to 100 nm.

An ink for inkjet printing can be obtained by adding a humectant as an essential component to the colored resin emulsion of the present invention. An inkjet printing ink comprising the colored resin emulsion of the present invention and a humectant is also one of the present invention. Examples of the humectant include glycerin, ethylene glycol, diethylene glycol, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, and the like.

[0051]

The present invention will be described in more detail with reference to the following 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, 194 parts by weight of deionized water, and
A flask was charged with 10 parts by weight of n-butoxymethylacrylamide, and the solution was heated to 50 ° C. while stirring under a nitrogen stream.
Raised to. Next, an ethanol solution 10 containing 0.5 parts by weight of V-70 (manufactured by Wako Pure Chemical Industries, oil-soluble azo polymerization initiator) was prepared.
A part by weight was poured into the flask, and immediately, a dye solution having the following composition was dropped over 2 hours.

<Composition of Dye Solution> n-butoxymethylacrylamide 89 parts by weight ethylene glycol dimethacrylate 1 part by weight Orazole Red G (manufactured by Ciba Geigy, metal complex of red azo dye) 20 parts by weight

After stirring at the same temperature for 3 hours, the mixture was cooled to room temperature to obtain a colored resin emulsion A. In the obtained emulsion A, 30 cerium acetylacetonate was added.
100 parts by weight of diethylene glycol dimethyl ether in which parts by weight were dissolved was added dropwise to the emulsion A over 1 hour with stirring, and then 6 g of 0.1N NaOH was added dropwise to hydrolyze cerium acetylacetonate and oxidize the fine particle surfaces. A cerium film was formed. After filtering the obtained colored resin emulsion with a filter having a pore size of 1 μm, a laser light scattering particle size distribution analyzer (manufactured by Otsuka Electronics Co., Ltd.)
When the particle diameter was measured by using, the average particle diameter was 92 n
m.

Example 2 After colored resin emulsion A was polymerized in the same manner as in Example 1, cerium oxide powder 20 was added to the obtained emulsion A.
Parts by weight of a mixed solution consisting of 100 parts by weight of n-butoxymethylacrylamide and 20 parts by weight of ethanol was added dropwise to Emulsion A over 1 hour with stirring.
C., and a cerium oxide film was formed on the surface of the fine particles.
The average particle size was 153 nm.

Comparative Example 1 A colored resin emulsion A was prepared in the same manner as in Example 1, and the obtained colored resin emulsion A was cast on a glass plate to a thickness of 1 μm. The average particle size was 81 nm.

The colored resin emulsions obtained in the respective Examples and Comparative Examples were evaluated as follows. The results are shown in Table 1. <Weather resistance> The emulsions of Examples 1 and 2 and Comparative Example 1 were cast on a 1.2 mm glass substrate to a thickness of 1 μm using a spin coater, and irradiated with a 750 W high-pressure mercury lamp from a distance of 50 cm for 10 hours. Then, a change in color was evaluated by a color difference (ΔE).

[0058]

[Table 1]

[0059]

Since the colored fine particles of the present invention have the above-mentioned constitution, a mixture of dyes having completely different chemical structures is uniformly and highly blended, and the resulting colored resin emulsion has high light resistance. Ink jet printing inks also have high light resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09B 67/02 C09B 69/04 69/04 C09D 11/00 C09D 11/00 B41J 3/04 101Y F term ( Reference) 2C056 EA13 FC01 2H086 BA53 BA56 BA59 BA60 4F070 AA35 AB09 AC13 AD05 AD07 AE03 AE04 CB02 CB12 4J002 BC011 BC041 BG051 BG061 BG071 BG121 BG131 BJ001 CD191 DE097 DE107 DE137 EE037 BE070707 EB009 EB009 EB286

Claims (7)

[Claims] 1. The following general formula (I): (In the formula, R ¹ represents a hydrogen atom or a methyl group, R ²
Represents an alkyl group having 3 to 6 carbon atoms), a core comprising a polymer and an oil-soluble dye, which is a polymerization raw material containing a monomer composition containing at least 30% by weight of a monomer represented by the formula: Colored fine particles comprising a shell layer containing an absorbent or an ultraviolet reflective agent. 2. The colored fine particles according to claim 1, wherein the shell layer contains an inorganic ultraviolet absorber or an ultraviolet reflector. 3. The colored fine particles according to claim 1, wherein the shell layer contains an organic ultraviolet absorber. 4. An oil-soluble dye, comprising: an anionic dye;
General formula (II):(Where R^Three Represents a hydrogen atom or a methyl group;^Four ,
R^Five , R⁶ Are the same or different and have 1 to 8 carbon atoms
Kill group, aralkyl group having 1 to 8 carbon atoms or 4 to 8 carbon atoms
X represents a halogen atom.
Then R^Four , R^Five , R ⁶ Of the number of carbon atoms contained in the group represented by
A total of 8 or more)
Characterized in that it is a salt obtained by reacting
The colored fine particles according to claim 1, 2 or 3. 5. The colored fine particles according to claim 1, wherein the average particle diameter is 200 nm or less. 6. A colored resin emulsion comprising the colored fine particles according to claim 5 dispersed in an aqueous solvent. 7. An ink for ink-jet printing, comprising the colored resin emulsion according to claim 6 and a humectant.