JP2002053790A - Colored resin fine particle, coating material and ink using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide colored resin particles which are red to yellow, has sufficient coloring power, can give a clear tone and, simultaneously, excels in chroma as well, and a coating material and an inkjet ink and the like which use these colored resin particles. SOLUTION: The colored resin fine particles comprise a colorant, and the colorant contains at least one kind of a styryl based dye to be represented by the formula (wherein R1 is a hydrogen atom or a cyano group; R2 is an alkyl group which may be substituted, an alkoxy group which may be substituted or a halogen atom; n is an integer of 0-2; when a plurality of R2 are present, each R2 may be the same or different; and R3 and R4 are each independently a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an aryl group which may be substituted or a cycloalkyl group) and have an average particle diameter of 20-500 nm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to colored resin fine particles having high transparency, high density and high saturation when used as an aqueous ink or the like. In particular, excellent characteristics are obtained when the ink is applied to the above ink.

[0002]

2. Description of the Related Art As a functional resin fine particle, a method of producing colored resin fine particles colored with a dye or pigment, for example, a method of obtaining colored resin fine particles by performing suspension polymerization or emulsion polymerization with a dye or a pigment, or a method of producing a colorless resin fine particle by a dye. And the like. However, in the method of obtaining colored resin fine particles by suspension polymerization, fine particles having an average particle diameter of about 5 μm or more are obtained, which is not preferable because it is too large as a coloring agent for paints and inks. On the other hand, in the emulsion polymerization method, the average particle diameter is 500 n.
m or less, but have the disadvantage that the range of dyes that can be selected is narrow, and the coloring power is low due to the low dye content. The method of obtaining colored resin fine particles by dyeing colorless resin fine particles is relatively easy to control the average particle diameter, and the selection range of the dye is relatively wide,
Although the dye content can be relatively high, it is necessary to go through a complicated dyeing process in order to obtain colored resin fine particles, which is inferior in practical use. Therefore, there has been a demand for a method which can easily produce colored resin fine particles containing a dye at a high concentration and having sufficient coloring power and a small average particle system.

On the other hand, in Examples 120 to 122 of WO 99/40123, a method of producing such colored resin fine particles by a mini-emulsion polymerization method using a phthalocyanine dye is proposed. In the case of yellow or red, only a dye concentration of about 10% can be realized, and in the case of yellow or red, which has a sufficient coloring power, Had not been reported.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has a sufficient coloring power and a sharp color by containing a coloring agent of red or yellow in a sufficiently high concentration. It is an object of the present invention to provide colored resin fine particles capable of giving an excellent color tone and excellent in chroma, and a paint, an inkjet ink and the like using the same.

[0005]

As a result of various studies, the present inventors have found that if miniemulsion polymerization is carried out using a styryl dye, fine particles having a sufficient coloring power in a yellow to red hue can be obtained. It has been found that dyes which could not be realized by yellow to red can obtain colored fine particles having a high concentration of 20% or more. Further, they have found that colored resin fine particles having a small particle diameter which can be used for paints and inks can be produced practically.

That is, the gist of the present invention is a colored resin fine particle containing a colorant, wherein at least one styryl dye represented by the following general formula (1) is contained as the colorant, and The gist of the present invention is a colored resin fine particle having a particle diameter of 20 to 500 nm.

[0007]

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(Wherein R ¹ represents a hydrogen atom or a cyano group, R ² represents an optionally substituted alkyl group, an optionally substituted alkoxy group or a halogen atom, and n represents 0 to 2 represents an integer, if R ² there are a plurality, each R ² may be different even in the same.
R ³ and R ⁴ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group or a cycloalkyl group. )

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a styryl dye represented by the above general formula is used as a coloring agent. In the general formula (1), the alkyl group which may be substituted in R ² is preferably an alkyl group having 1 to 20 carbon atoms. Preferably has 1 to 20 carbon atoms. Also,
Examples of the group which may be substituted on the alkyl group, the alkoxy group or the aryl group include a halogen atom, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, and the like.When the substituent is an organic group, The substituent preferably has 1 to 20 carbon atoms.
R ² may be a halogen atom, but is preferably a chlorine atom. Among them, when R ² is present, it is preferably an alkyl group or a halogen atom, and most preferably a methyl group. Further, n is desirably 0 or 1.

Most preferably, there is no substituent on the benzene ring, ie, when n = 0, or there is one substituent on the benzene ring, ie, n = 1, and R ² is a methyl group. Is most preferred. As the optionally substituted alkyl group for R ³ or R ⁴ , the alkyl group preferably has 1 to 20 carbon atoms. As the optionally substituted alkenyl group, the alkenyl group may have 1 to 20 carbon atoms. It is desirable that Also, an alkyl group, an alkenyl group,
Examples of the group that may be substituted on the aryl group include a halogen atom, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a tetrahydrofurfuryl group, and the like.When the substituent is an organic group,
The substituent preferably has 1 to 20 carbon atoms.

Specifically, R ³ and R ⁴ are methyl groups,
Lower alkyl groups such as ethyl group, linear or branched propyl group and butyl group; phenethyl group, benzyl group,
An aralkyl group such as a phenylpropyl group; a phenyl group, p
An aryl group such as -chlorophenyl group; a cyclohexyl group; a lower alkoxy lower alkyl group such as a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, a butoxyethyl group, a γ-methoxybutyl group; a methoxyethoxyethyl group, an ethoxyethoxyethyl group, Lower alkoxy lower alkyl group such as propoxyethoxyethyl group; hydroxy lower alkyl group such as hydroxyethyl group, β-hydroxypropyl group, β-hydroxybutyl group; chloroethyl group, chloropropyl group, bromoethyl group, iodoethyl group, etc. Halogeno lower alkyl group; cyano lower alkyl group such as cyanomethyl group, cyanoethyl group, cyanopropyl group; tetrahydrofurfuryl group; alkenyloxy group such as allyloxyethyl group and 2-methylallyloxyethyl group Grade alkyl group; a benzyloxy ethyl group; phenylalanine oxyethyl group, p- chloro full aryloxy-lower alkyl groups such as enyl oxyethyl group
Aralkyloxy lower alkyl groups such as phenethyloxyethyl group; lower alkoxycarbonyl lower alkyl groups such as methoxycarbonylethyl group, ethoxycarbonylethyl group, propoxycarbonylethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group; acetoxyethyl group Lower alkylcarbonyloxy lower alkyl groups such as propionyloxyethyl group, β-acetoxypropyl group, β-acetoxybutyl group; methoxycarbonyloxyethyl group; lower alkoxycarbonyloxy lower alkyl groups such as ethoxycarbonyloxyethyl group; tetrahydrofur And a tetrahydrofurfuryloxy lower alkyl group such as a furyloxyethyl group.

Particularly preferred R ³ and R ⁴ are C _1-6 alkyl, phenethyl, γ-methoxybutyl, chloroethyl, benzyl, methoxyethyl, methoxyethoxyethyl, cyanoethyl, tetrahydrofurfuryl. Phenyl, cyclohexyl, phenethyloxyethyl, phenoxyethyl, allyloxyethyl, tetrahydrofurfuryloxyethyl, hydroxyethyl, methoxycarbonylethyl, acetoxyethyl and the like.

Among them, most preferred is a case where R ³ is an alkyl group and R ⁴ is a substituted alkyl group. As a specific example of such a styryl dye,
The following dyes may be mentioned.

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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The styryl dye of the present invention can be synthesized by a known method. For example, when R ¹ is a cyano group, that is, in the case of a tricyanovinyl dye, it can be obtained by the method described in JP-A-60-31563, and tetracyanoethylene is added to an aniline in an organic solvent. , And the target substance precipitated after the reaction can be easily obtained by filtration.

When R ¹ is a hydrogen atom, that is, in the case of a dicyanovinyl dye, for example, Japanese Patent Publication No. 4-61797
As described in the official gazette,

[0025]

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(The definitions of R ² , R ^3, R ⁴ and n are the same as those in the general formula (1)), and malononitrile is dissolved in an organic solvent such as ethanol or N, N-dimethylformamide. And, after the reaction, the target substance precipitated can be easily obtained by filtration. In the present application, in addition to the above styryl-based dye as a colorant, other dyes can be appropriately combined and used as needed in the colored resin fine particles.

Dyes that can be used in combination with styryl dyes include, for example, direct dyes, acid dyes,
Basic dyes, azoic dyes, disperse dyes, oil-soluble dyes,
It can be appropriately selected and used according to the type of the monomer to be used from among reactive dyes, fluorescent dyes and the like. Among them, oil-soluble dyes are particularly preferable, and specific examples thereof include, for example, C.I. I. Solvent Yellow 1
6, 21, 25, 29, 33, 56, 8
2, 88, 89, 150, 151, 163
And C.I. I. Solvent Orange 14, 37
40, 44, 45, etc., also for magenta,
For example, C.I. I. Solvent Red 24, 27 and the like, and C.I. I. Solvent Violet 13, 14, 14, 21, 27, etc., which are azo (monoazo, disazo, trisazo, etc.), triphenylmethane, phthalocyanine, anthraquinone, or styryl. Are more preferable, and azo or styryl is particularly preferable.

The colored resin fine particles of the present invention are fine particles containing a styryl dye in a polymerizable monomer which functions as a binder. The polymerizable monomer in the present invention is preferably a vinyl polymer, and the polymerizable monomer constituting the polymer is not particularly limited, and conventionally, for example, emulsion polymerization of colored resin fine particles Various monomers used for the above are used.

In the present invention, specific examples of the vinyl monomer constituting the vinyl polymer include:
Styrene, α-methylstyrene, α-substituted styrene such as α-ethylstyrene, m-methylstyrene, p-methylstyrene, nuclear-substituted styrene such as 2,5-dimethylstyrene, p-chlorostyrene, p-bromostyrene, Vinyl aromatics such as nuclear-substituted halogenated styrenes such as dibromostyrene, (meth) acrylic acid ("(meth) acryl" means acryl and methacryl, and the same applies hereinafter); Crotonic acid, maleic acid,
Unsaturated carboxylic acids such as fumaric acid, citraconic acid and itaconic acid, methyl (meth) acrylate, ethyl (meth)
Unsaturated carboxylic acids such as acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, and benzyl (meth) acrylate Acid esters, (meth) acrylaldehyde, unsaturated carboxylic acid derivatives such as (meth) acrylonitrile, (meth) acrylamide, N-vinyl compounds such as N-vinylpyridine, N-vinylpyrrolidone, vinyl formate,
Vinyl esters such as vinyl acetate and vinyl propionate; vinyl halides such as vinyl chloride, vinyl bromide and vinylidene chloride; allyl alcohol, allyl methyl ether, allyl ethyl ether, allyl methyl ketone, allyl acetic acid, allyl phenol, etc. Allyl compounds, N-methylolacrylamide, N-ethylolacrylamide, N-propanolacrylamide, N-
N-substituted unsaturated amides such as methylol maleamic acid, N-methylol maleamic acid ester, N-methylol maleimide, N-ethylol maleimide, conjugated dienes such as butadiene and isoprene, divinylbenzene, divinylnaphthalene, divinylcyclohexane Polyfunctional vinyl compounds such as ethylene glycol di (meth)
Acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Hexamethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol di (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) ac Rate, sorbitol penta (meth) acrylate, multifunctional acrylates such as sorbitol hexa (meth) acrylate.
Among these, N-substituted unsaturated amides, conjugated dienes, polyfunctional vinyl compounds, polyfunctional acrylates, and the like can also cause a cross-linking reaction in the produced polymer.

The polymer constituting the colored resin fine particles of the present invention is typically a styrene homopolymer, (meth)
Acrylate homopolymer, styrene- (meth) acrylate copolymer, styrene- (meth) acrylate- (meth) acrylic acid copolymer, (meth)
An acrylate- (meth) acrylic acid copolymer is exemplified.

The colored resin fine particles of the present invention have an average particle diameter of 20 to 500 nm, and particularly preferably 20 to 300 nm.
nm, particularly preferably 20 to 200 nm. If the average particle size is more than the above range, the effect of the present invention as the colorant-containing polymer fine particles cannot be obtained, while if the average particle size is less than the above range, a large amount of surfactant or the like is contained in the fine particle dispersion due to production of the polymer fine particles. , Which adversely affect the quality of the organic pigment. Here, the average particle diameter is a volume average particle diameter measured by a light Doppler type particle size distribution meter (“MICROTRAC particle size distribution meter” manufactured by Nikkiso Co., Ltd.).

The colored resin fine particles of the present invention can be produced by a usual emulsion polymerization method. The oil phase containing a polymerizable monomer and a styryl dye as a colorant as described above is treated with a surfactant. A colorant-containing monomer emulsion by emulsifying in water in the presence of a coloring agent, and then polymerizing the monomer in the presence of a polymerization initiator to form a colorant-containing polymer emulsion. Is preferred because a high content of a colorant can be contained in the polymer fine particles.

Here, the surfactant used is:
There is no particular limitation, and various surfactants such as anionic surfactants, cationic surfactants, and nonionic surfactants conventionally used in emulsion polymerization can be used. Specific examples of the anionic surfactant include higher fatty acid salts such as sodium laurate, sodium stearate, and sodium oleate, sodium dodecyl sulfate, sodium lauryl sulfate, cetyl sulfate, sodium stearyl sulfate, and oleyl. Alkyl sulfates such as sodium sulfate, higher alcohol sulfates such as sodium octyl alcohol sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, aliphatic alcohol sulfates such as sodium acetyl alcohol sulfate, laurylbenzene Sodium sulfonate, sodium cetylbenzenesulfonate, sodium stearylbenzenesulfonate, oleylbenzenesulfone Alkyl benzene sulfonates such as sodium, alkyl naphthalene sulfonates such as sodium isopropyl naphthalene sulfonate, alkyl diphenyl ether disulfonates such as sodium alkyl diphenyl ether disulfonate, alkyl phosphate salts such as sodium lauryl phosphate, sodium stearyl phosphate, lauryl ether Polyethylene oxide adducts of sodium sulfate, polyethylene oxide adducts of ammonium lauryl ether sulfate, polyethylene oxide adducts of alkyl ether sulfates such as polyethylene oxide adducts of lauryl ether triethanolamine,
Polyethylene oxide adducts of alkyl phenyl ether sulfate such as polyethylene oxide adduct of sodium nonyl phenyl ether sulfate, polyethylene oxide adducts of alkyl ether phosphate such as polyethylene oxide adduct of sodium lauryl ether phosphate, nonyl phenyl ether phosphoric acid Examples include alkylphenyl ether phosphate polyethylene oxide adducts such as sodium polyethylene oxide adduct.

Specific examples of the cationic surfactant include, for example, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride. , Quaternary ammonium salts such as lanolin-derived quaternary ammonium salts, lauryl pyridinium chloride, lauryl pyridinium bromide, pyridinium salts such as cetyl pyridinium chloride, imidazolinium salts such as 2-stearyl-hydroxyethyl-2-imidazoline derivatives, N, N-diethyl-stearamide-methylamine hydrochloride, polyoxyethylene stearylamine, etc. Mention may be made of the Min salts and the like.

Specific examples of the nonionic surfactant include polyethylene glycol alkyl ethers such as polyethylene glycol cetyl ether, polyethylene glycol stearyl ether, polyethylene glycol oleyl ether, and polyethylene glycol behenyl ether; and polyethylene glycol polypropylene. Polyethylene glycol polypropylene glycol alkyl ethers such as glycol cetyl ether and polyethylene glycol polypropylene glycol decyl tetradecyl ether; polyethylene glycol alkyl phenyl ethers such as polyethylene glycol octyl phenyl ether and polyethylene glycol nonyl phenyl ether; ethylene glycol monostearate; Ethylene glycol, diethylene glycol stearate, polyethylene glycol distearate, polyethylene glycol monolaurate,
Polyethylene glycol fatty acid esters such as polyethylene glycol monostearate and polyethylene glycol monooleate, glycerin fatty acid esters such as glyceryl monomyristate, glyceryl monostearate, glyceryl monoisostearate, glyceryl distearate and glyceryl dioleate, monopalmitin Sorbitan acid esters, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, etc., polyethylene oxide adducts of glyceryl monostearate, polyethylene oxide adducts of glyceryl monooleate, etc. Polyethylene oxide adducts of glycerin fatty acid ester, polyethylene of sorbitan monopalmitate Polyethylene sorbitan fatty acid esters such as oxide adducts, polyethylene oxide adducts of sorbitan monostearate, polyethylene oxide adducts of sorbitan tristearate, polyethylene oxide adducts of sorbitan monooleate, and polyethylene oxide adducts of sorbitan trioleate Polyethylene sorbite fatty acid esters such as oxide adducts, polyethylene oxide adducts of sorbite monolaurate, polyethylene oxide adducts of sorbite tetrastearate, polyethylene oxide adducts of sorbite hexastearate, and polyethylene oxide adducts of sorbite tetraoleate. Oxide adducts and castor oil polyethylene oxide adducts can be mentioned.

In the present invention, a co-surfactant is added to the surfactant in order to keep the average particle size of the oil phase containing the polymerizable monomer and the styryl dye in the specific range described below. It is preferable that they coexist. As the co-surfactant, those which are water-insoluble or hardly soluble and are monomer-soluble and which are used in a conventionally known "mini-emulsion polymerization" described later in detail can be used. Suitable co-surfactants include, for example, dodecane,
Alkanes having 8 to 30 carbon atoms such as hexadecane and octadecane; alkyl alcohols having 8 to 30 carbon atoms such as lauryl alcohol, cetyl alcohol and stearyl alcohol; lauryl (meth) acrylate, cetyl (meth) acrylate, and stearyl (meth) Alkyl (meth) acrylates having 8 to 30 carbon atoms such as acrylate,
Examples thereof include alkyl thiols having 8 to 30 carbon atoms such as lauryl mercaptan, cetyl mercaptan, and stearyl mercaptan, and polymers or polyadducts such as polystyrene and polymethyl methacrylate, carboxylic acids, ketones, and amines.

In the method for producing colored resin fine particles, which is preferable in the present invention, first, the monomer and the styryl-based dye are added in the presence of the surfactant and, if necessary, in the presence of the co-surfactant. And emulsified in water to form a colorant-containing monomer emulsion. The content of the styryl-based dye as a colorant in the colored resin fine particles of the present invention is as follows.
It is usually in the range of 0.01 to 60 parts by weight with respect to 0 parts by weight, but in order to obtain colored resin fine particles having sufficient coloring power, the styryl dye is preferably 10 parts by weight or more, and more preferably. When the amount is 15 parts by weight or more, most preferably 20 parts by weight or more, particularly excellent colored resin fine particles can be realized.

Here, to form the colored resin fine particles, for example, a polymerizable monomer solution to which a styryl dye or a co-surfactant is further added as a coloring agent, and an aqueous solution of the surfactant are mixed with a piston. The mixture is uniformly mixed and emulsified by a homogenizer, a microfluidizer (for example, “Microfluidizer” manufactured by Microfluidics Co., Ltd.), or a shear mixer such as an ultrasonic disperser. At that time, the charged amount of the polymerizable monomer with respect to water is about 0.1 to 50% by weight based on the total amount with water, and the amount of the surfactant used is
The amount of the monomer is preferably 0.01 to 100 parts by weight.
Not less than the critical micelle concentration (CMC) in the presence of the emulsion to be formed, and the amount of the cosurfactant used is preferably 100 parts by weight of the monomer. 0.1 to 40 parts by weight, more preferably 0.1 to 10 parts by weight.

The particle diameter of the monomer droplets in the colored resin fine particles of the present invention is 20 to 20 as the above-mentioned volume average particle diameter.
The thickness is preferably 500 nm, more preferably 20 to 300 nm, and particularly preferably 20 to 200 nm. Next, the method for producing colored resin fine particles, which is preferable in the present invention, is characterized in that the colorant-containing monomer emulsion is formed into a resin emulsion by polymerizing the monomer in the presence of a polymerization initiator, thereby forming colored fine particles. Get.

Here, in order to polymerize the monomer emulsion in the presence of a polymerization initiator to form a resin emulsion, for example, a polymerizable monomer solution to which the above-mentioned colorant or co-surfactant is added is used. Alternatively, in any one of the above-mentioned aqueous solutions of the surfactant, based on 100 parts by weight of the monomer, preferably 0.1 to 30 parts by weight, more preferably 0.1 to 30 parts by weight.
10 parts by weight of a polymerization initiator is added in advance, and polymerization is carried out at a temperature of preferably 30 to 95 ° C, more preferably 50 to 95 ° C, for usually 1 to 6 hours.

Here, the polymerization initiator is not particularly limited, and those conventionally used for radical polymerization and the like can be used, and a polymerization initiator soluble in a monomer, Both of the polymerization initiator which is hardly soluble in the monomer can be used without limitation. Specifically, for example, 2,2 '
-Azobis (2-methylpropionitrile), 2,2 ′
-Azobis (2-methylbutyronitrile), 2,2'-
Azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 1,1′-azobis ( Cyclohexanecarbonitrile), 2,2'-azobis (2-amidinopropane)
Azobisnitrile such as hydrochloride, acetyl peroxide, octanoyl peroxide, 3,5,5
Diacyl peroxide such as trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, di-t
Dibutyl peroxide such as -butyl peroxide, t-butyl-α-cumyl peroxide, dicumyl peroxide, t-butyl peroxyacetate, α-
Cumyl peroxy pivalate, t-butyl peroxy octoate, t-butyl peroxy neodecanoate,
peroxyesters such as t-butyl peroxy laurate, t-butyl peroxybenzoate, di-t-butyl peroxyphthalate, di-t-butyl peroxyisophthalate, t-butyl hydroperoxide,
Organic peroxides such as hydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide, cumene hydroperoxide and di-isopropylbenzene hydroperoxide, and peroxycarbonates such as t-butylperoxyisopropyl carbonate. And radical polymerization initiators such as inorganic peroxides such as hydrogen peroxide and persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate. These may be used in combination of two or more, or may be used in combination with a redox polymerization initiator.

In the present invention, the amount of the above-mentioned monomer in the presence of a polymerization initiator of a monomer emulsion by using a surfactant in an amount less than the critical micelle concentration (CMC) and a co-surfactant is used. The polymerization is, for example, PLTang, EDSudol,
CASilebi, MSEl-Aasser; J. Appl. Polym. Sci., No. 43
Vol., P. 1059 (1991), which is known as so-called "mini-emulsion polymerization" and has a particle size of about several μm in the presence of a surfactant having a critical micelle concentration (CMC) or more. The conventional emulsion polymerization, in which an aqueous emulsion of monomer droplets is polymerized using a water-soluble polymerization initiator, starts polymerization in surfactant micelles, and supplies the monomer by diffusion from the monomer droplets. In contrast, in “mini-emulsion polymerization”, uniform polymer fine particles are formed because the monomer is polymerized in the monomer droplets, while the polymer fine particles grow and are formed. In the case of using a colorant as in the present invention, in the conventional emulsion polymerization, at the monomer emulsion stage, the colorant present in the monomer droplets has a water solubility with the monomer. Of the monomer, the monomer is simply diffused into the micelle and polymerized. On the other hand, in the “mini-emulsion polymerization”, there is no need to diffuse the monomer in the polymerization process, so the difference is that the colorant can be present in the polymer fine particles as it is. Occurs.

Further, for example, JSGuo, MSEl-Aasser, J.
W.Vanderhoff; J.Polym.Sci.: Polym.Chem.Ed., Vol.27,6
The so-called "microemulsion polymerization" of particles having a particle size of 5 to 50 nm described in page 91 (1989) and the like is obtained by using a large amount of a surfactant having a critical micelle concentration (CMC) or more. There is a problem that a large amount of surfactant is mixed in the polymer fine particles, or that a large amount of time is required for steps such as water washing, acid washing, and alkali washing for removing the surfactant.

In the present invention, after the polymerization, the surface of the polymer fine particles may be crosslinked by heat treatment or the like for the purpose of suppressing bleeding of the colorant from the surface of the colored resin fine particles. Incidentally, the used surfactants and the like can be removed by water washing, acid washing, alkali washing or the like as necessary. In the production of the colored resin fine particles of the present invention, various known additives such as an antioxidant and an ultraviolet absorber used for the seed polymer fine particles may be added to the emulsion, if necessary.

[0045]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. Dye Synthesis Example 1 A styryl-based magenta dye represented by the following structural formula (I) was synthesized by the following method.

[0046]

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Dye Synthesis Example 2 A styryl yellow dye represented by the following structural formula (II) was prepared by the following method.

[0048]

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Example 1 10.4 g of methyl methacrylate, 0.8 of methacrylic acid
4.8 g of the styryl-based magenta dye (I) obtained in Dye Synthesis Example 1, 0.8 g of co-surfactant (co-stabilizer) stearyl methacrylate, and 0.1 g of azobisisobutyronitrile oil-soluble initiator. 48 g was stirred and mixed to form a uniform solution, and the solution was added dropwise with stirring to an aqueous solution in which 1.47 g of sodium dodecyl sulfate was dissolved in 64 g of demineralized water. After the completion of the dropping, the mixture was further stirred with a stirrer for 10 minutes. The red dispersion obtained in this manner was converted into an ultrasonic disperser (“UL
TRASONIC HOMOGENIZER UH-6
00 ") for 20 minutes to produce a red, styryl-based dye-containing monomer emulsion.

The obtained monomer emulsion was stirred with a stirrer,
200 mL capacity 4 equipped with a cooler and thermometer
The mixture was transferred to a single-necked flask, and the temperature was raised to 60 ° C. under a nitrogen stream to start polymerization. After 3 hours, the polymerization was terminated, and the dye was contained in the methyl methacrylate polymer particles.
A methyl methacrylate polymer emulsion containing a styryl-based magenta dye was prepared. The particle diameter of the polymer particles of the obtained emulsion was measured by a light Doppler type particle size distribution meter (“MICROTRAC particle size distribution meter” manufactured by Nikkiso Co., Ltd.), and as a result, the volume average particle size was about 44 nm. The obtained polymer particles contained 30 parts by weight of the styryl-based magenta dye based on 100 parts by weight of the polymer particles, and the conversion of methyl methacrylate was 93%. Example 2 12 g of styrene, 0.8 g of methacrylic acid, Dye Synthesis Example 2
3.2 g of the styryl yellow dye (II) obtained in
0.32 g of co-surfactant (co-stabilizer) hexadecane,
And oil-soluble initiator azobisisobutyronitrile 0.48
g was stirred and mixed to form a homogeneous solution, and the solution was added dropwise with stirring to an aqueous solution in which 2.21 g of sodium dodecyl sulfate was dissolved in 64 g of demineralized water. After the addition was completed, the mixture was further stirred with a stirrer for 10 minutes. The yellow dispersion obtained by the above method is supplied to an ultrasonic disperser (“ULTRASONIC HOM” manufactured by SMT).
OGENIZER UH-600 ") for 20 minutes to prepare a yellow, styryl-based yellow dye-containing monomer emulsion.

The obtained monomer emulsion was stirred with a stirrer,
200 mL capacity 4 equipped with a cooler and thermometer
The mixture was transferred to a one-necked flask and heated to 60 ° C. under a nitrogen stream to start polymerization. After 3.5 hours, the polymerization was terminated, and a yellow, styryl yellow containing a dye in the styrene polymer particles was used. A styrene polymer emulsion containing a dye was prepared. The particle size of the polymer particles of the obtained emulsion was measured using a light Doppler type particle size distribution meter (“MICROT” manufactured by Nikkiso Co., Ltd.).
The particle size was about 65 nm as measured by a RAC particle size distribution analyzer ”). The conversion of styrene was 94
%Met. Example 3 10.4 g of methyl methacrylate, 0.8 of methacrylic acid
g, styryl-based magenta dye (I) used in Example 1
4.8 g and co-surfactant (co-stabilizer) 0.8 g of stearyl methacrylate were stirred and mixed at room temperature to form a homogeneous solution. The solution was added to 60 g of demineralized water, 1.47 g of sodium dodecyl sulfate and sodium hydrogen carbonate. 0.162 g was added dropwise with stirring to an aqueous solution in which 0.162 g was dissolved.
The red dispersion obtained by stirring for 10 minutes with a stirrer is
Ultrasonic disperser ("ULTRASONIC H" manufactured by SMT)
OMOGENIZER UH-600 ") for 20 minutes to produce a red styryl dye-containing monomer emulsion.

The obtained monomer emulsion was stirred with a stirrer,
200 mL capacity 4 equipped with a cooler and thermometer
After the temperature was raised to 60 ° C. under a nitrogen stream, polymerization was started by adding an aqueous solution in which 0.48 g of potassium persulfate was dissolved in 4 g of demineralized water, and the polymerization was terminated after 2 hours. A red, styryl-based magenta dye-containing methyl methacrylate polymer emulsion containing a dye in the methyl methacrylate polymer particles was prepared. When the particle size of the polymer particles of the obtained emulsion was measured with a light Doppler type particle size distribution meter (“MICROTRAC particle size distribution meter” manufactured by Nikkiso Co., Ltd.), the volume average particle size was about 43 nm.
Met. The obtained polymer particles contained 30 parts by weight of the styryl-based magenta dye based on 100 parts by weight of the polymer particles, and the conversion of methyl methacrylate was 98%.

[0053]

According to the present invention, by containing a coloring agent in a red or yellow color at a sufficiently high concentration, it has a sufficient coloring power, can give a clear color tone, and has excellent chroma. Colored resin fine particles can be obtained, and by using this, excellent paints and ink jet inks can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 7/12 C09D 7/12 4J039 11/00 11/00 201/00 201/00 (72) Inventor Takeshita Kimiya, 1000, Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Inside the Yokohama Research Laboratory, Mitsubishi Chemical Corporation (72) Inventor Munehiro Sakamoto 1000, Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture F-term in Yokohama Research Laboratory, Mitsubishi Chemical Corporation (reference) 4H056 CA02 CC02 CD08 CE02 4J002 AA011 BC031 BC071 BG021 BG031 ET006 FD096 4J011 PA39 PB25 PC02 PC06 4J037 AA30 CB28 CC13 DD05 EE08 EE12 FF03 4J038 CC022 CC07 CC02 CG02 CG03 CG03 CG03 CG03 CG03 CG03 CG03 CG03 CG03 CG03 CG03 CG022 CG03 AD09 AD10 AD11 AD12 AD23 BC44 BE02 BE22 EA42 GA24

Claims (7)

[Claims] 1. A colored resin fine particle containing a colorant, which contains at least one styryl dye represented by the following general formula (1) as the colorant, and has an average particle diameter of 20 to 500 nm. Colored resin fine particles, characterized in that: Embedded image (Wherein, R ¹ represents a hydrogen atom or a cyano group, and R ² is
Represents an alkyl group which may be substituted, an alkoxy group which may be substituted or a halogen atom;
Represents an integer, if R ² there are a plurality, each R ² may be different even in the same. R ³ and R ⁴ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group or a cycloalkyl group. ) 2. The colored resin fine particles according to claim 1, wherein a styryl dye is contained in an amount of 10% by weight or more based on 100 parts by weight of the colored resin fine particles. 3. The colored resin fine particles according to claim 1, wherein the resin is a vinyl resin. 4. An oil phase containing a polymerizable monomer and a styryl dye is emulsified in water in the presence of a surfactant to form a colorant-containing monomer emulsion. The colored resin fine particles according to claim 1, wherein the monomer is polymerized in the presence to form a colorant-containing emulsion. 5. A paint comprising the colored resin fine particles according to claim 1. Description: 6. An ink comprising the colored resin fine particles according to claim 1. Description: 7. An ink jet recording liquid comprising the colored resin fine particles according to claim 1. Description: