WO2001027166A1

WO2001027166A1 - Emulsion of colored fine particles

Info

Publication number: WO2001027166A1
Application number: PCT/JP2000/007058
Authority: WO
Inventors: Tokushige Shichiri; Masahiro Ishii; Yoshiyuki Oguchi
Original assignee: Sekisui Chemical Co., Ltd.
Priority date: 1999-10-12
Filing date: 2000-10-11
Publication date: 2001-04-19
Also published as: AU7683800A

Abstract

An emulsion of colored fine particles which has a high color density and has excellent impact stability because the fine particles are less apt to coagulate due to surface crosslinking; an ink for ink-jet printing which comprises the emulsion of colored fine particles; a color filter for liquid-crystal displays; an emulsion of colored fine particles which is for electrodeposition color filters; and colored fine particles. The emulsion of colored fine particles comprises an aqueous medium and dispersed therein colored fine particles obtained by polymerizing a colored composition comprising a monomer composition and a colorant. The monomer composition comprises at least 10 wt.% monomer represented by general formula (I)(wherein R1 represents hydrogen or methyl; and R2 represents C¿3-6? alkyl). The colored fine particles have crosslinked structures formed at least on the surface.

Description

Specification

Colored particle emulsion technology

The present invention relates to a colored fine particle emulsion having high color density, high stability of fine particles, and excellent stability against impact, etc., an ink for ink jet printing comprising the colored fine particle emulsion, and a color for a liquid crystal display. The present invention relates to a filter, a colored fine particle emulsion for an electrodeposited color filter, and a colored fine particle. Background art

Colored fine particle emulsions in which colored fine particles are dispersed are used for various coatings, inks for writing instruments, printing inks, inks for inkjet printing, and the like. With ordinary inks and colored emulsions, it is difficult to achieve a spectral spectrum of one primary color with one type of dye, and toning is usually performed by mixing several types 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, or an azo metal complex-based yellow dye and a phthalocyanine-based cyan dye are mixed. As can be seen from these examples, these materials are mixtures of dyes having completely different chemical structures. Therefore, when preparing an emulsion containing these dye mixtures, the monomer composition used therein must be capable of dissolving all the constituent dyes at a high concentration. If there is a difference in solubility depending on the dye, the dye precipitates during the production of fine particles, causing problems such as turbidity of the coating film and insufficient color density of the coating film.

In addition, when a colored emulsion is used as an ink for ink-jet printing, a strong mechanical impact is applied to the ink when the ink is ejected from the nozzle, so that coalescence of fine particles is likely to occur. For this reason, high impact stability is required when colored emulsions are used in ink jet printing inks.

One of the conventionally known methods for producing colored fine particles is, for example, emulsion polymerization of vinyl chloride alone or a monomer copolymerizable with vinyl chloride and vinyl chloride. A method is known in which polymer fine particles are produced by the above method, and dyed with a dye and a dyeing assistant to produce colored fine particles.

However, with such a method, it was difficult to produce colored fine particles containing a dye at a high concentration.

For example, Japanese Patent Application Laid-Open No. 55-139471 discloses an ink jet printing ink composition in which a polymer latex is impregnated with a disperse dye. However, this method has a disadvantage that the color density is not sufficient because the disperse dye does not sufficiently impregnate the polymer latex and only the surface of the polymer latex is dyed depending on the dye used.

JP-A-54-58504 discloses a method for producing colored fine particles by mixing an oil-soluble dye composition with vinyl polymer particles. In this method, when the oil-soluble dye composition is added to the aqueous dispersion of vinyl polymer particles, the vinyl polymer particles are easily aggregated, and the dye is not sufficiently impregnated into the vinyl polymer particles, resulting in a low color density. There is a problem that.

Japanese Patent Application Laid-Open No. 62-953666 discloses that an oil-soluble dye and a polymer composition are dissolved in a hydrophobic organic solvent, and a surfactant and water are added, mixed, and emulsified. Accordingly, a method for producing colored fine particles is disclosed. In this method, there is a problem that the particle size does not become sufficiently small.Also, there is a problem that a surfactant is desorbed due to environmental changes such as concentration, pH, and mechanical shock, and the colored fine particles are easily aggregated. is there. Japanese Patent Application Laid-Open No. 62-172,076 discloses that a polymer comprising an insoluble polymer dispersed in a liquid medium, this polymer contains an oil-soluble dye, and a nonionic stabilizer is permanently A heterophasic ink composition having a configuration that is bonded to is disclosed. However, the permanent binding of the nonionic stabilizer alone does not provide sufficient stability and generally tends to increase the particle size.

Japanese Patent Publication No. 52-293336 discloses that one or more unsaturated monomers including butoxymethyl acrylamide and unsaturated monomers including vinyl chloride, styrene, etc. When performing copolymerization with one or more kinds, the dye is dissolved or dispersed in the unsaturated monomer, and then the unsaturated monomer is copolymerized, and the inside thereof is colored with the dye. A method for producing colored fine particles is disclosed. However, these colored fine particles do not take into account the physical properties required for ink jet printing, such as particle size and mechanical stability.

Examples of a method for forming a color filter of a liquid crystal display element include an electrodeposition method in addition to printing using the above-described ink jet. The electrodeposition method is an excellent method in that pattern formation accuracy is excellent and the process is relatively simple. As disclosed in Japanese Patent Application Laid-Open No. 8-229314, conventionally, in the electrodeposition method, melamine, epoxy, isocyanate, etc. are added to water-soluble resins such as acrylic resins and polyester resins containing an acid group. A method of using an electrodeposition solution in which a crosslinking agent and a pigment are blended is known. However, since the electrodeposited film is re-dissolvable, it is necessary to crosslink with light or heat for each color before electrodepositing the next color when obtaining pixels of multiple colors. there were. In addition, the electrodeposited color filter using a pigment has poor smoothness of the film surface, and has a problem in transparency. Further, since the ratio between the coloring agent and the binder resin changes depending on the ratio of the ionic group, adjustment is required. Summary of the Invention

In view of the above, the present invention provides a colored fine particle emulsion having a high color density and a small impaction of fine particles due to surface cross-linking and thus having excellent impact stability, an ink jet printing ink comprising the colored fine particle emulsion, and a liquid crystal display. An object of the present invention is to provide a color filter, an electrodeposited colored fine particle emulsion for a color filter, and a colored fine particle.

The present invention is a colored fine particle emulsion in which colored fine particles obtained by polymerizing a colored composition comprising a monomer composition and a coloring agent are dispersed in an aqueous medium, wherein the monomer composition is: The following general formula (I):

(I)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² is an alkyl having 3 to 6 carbon atoms. The colored fine particles contain 10% by weight or more of a monomer represented by the following formula (1), and the colored fine particles are colored fine particle emulsions having a crosslinked structure formed on at least the surface thereof.

The colorant is preferably an oil-soluble dye.

The coloring agent may further include an anionic dye and the following 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 1-8 carbon atoms, an aralkyl group having 1-8 carbon atoms or Represents a cycloalkyl group having 7 to 12 carbon atoms, X 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.) It is also preferable that the salt is obtained by reacting a thiothionic monomer.

The crosslinked structure preferably has a molecular weight between crosslinks of 500 or less. The monomer composition preferably contains a monomer having two or more vinyl groups.

The colored fine particles are obtained by further reacting a crosslinking agent with fine particles obtained by polymerizing a monomer composition containing a monomer having a functional group capable of reacting with a crosslinking agent and a coloring composition comprising a coloring agent. Preferably,

The colored fine particles were obtained by absorbing a monomer having two or more vinyl groups and an oil-soluble polymerization initiator to fine particles obtained by polymerizing a colored composition comprising a monomer composition and a coloring agent. Thereafter, it is also preferable to polymerize the above-mentioned monomer having two or more vinyl groups.

The monomer composition preferably contains 1 to 60% by weight of a vinyl monomer containing an epoxy group.

The colored fine particle emulsion of the present invention preferably contains an amine silane coupling agent. An ink-jet printing ink containing the colored fine particle emulsion of the present invention and a humectant is also one of the present invention.

A color filter for a liquid crystal display using the above ink jet printing ink is also one of the present invention.

The colored fine particle emulsion for an electrodeposition color filter containing the colored fine particle emulsion of the present invention and the electrolyte is also one of the present invention.

The colored fine particles obtained from the colored fine particle emulsion of the present invention are also one of the present invention. Detailed description of the invention

Hereinafter, the present invention will be described in detail.

The colored fine particle emulsion of the present invention is one in which colored fine particles obtained by polymerizing a colored composition comprising a monomer composition and a coloring agent are dispersed in an aqueous medium.

The colored fine particle emulsion of the present invention is characterized in that the colored fine particles dispersed in an aqueous medium have a crosslinked structure.

The colored fine particles may have a crosslinked structure all the way to the inside of the fine particles, or may have a structure in which only the surface of the fine particles has a crosslinked structure.

However, the colored fine particles have at least a crosslinked structure formed on the surface thereof.

When the colored fine particles have a crosslinked structure on the surface and inside, the degree of crosslinking between the surface and the inside may be uniform or may be uneven. When the degree of cross-linking is uniform up to the surface and inside, a cross-linked structure can usually be formed by a one-step reaction. When the colored fine particles have a bias in the degree of internal cross-linking, or when a cross-linked structure is formed only on the surface of the fine particles, the cross-linked structure is usually formed by a reaction including multiple steps. Is done.

The case where the colored fine particles have a uniform crosslinked structure on the surface and inside of the fine particles will be described in detail below.

When producing colored fine particles having a crosslinked structure throughout the fine particles, the above monomer composition is a vinyl-based monomer composition from the viewpoint of easy particle size control and production efficiency, and emulsification. It is preferable to obtain colored fine particles by polymerization.

The vinyl monomer contained in the vinyl monomer composition is not particularly limited as long as it can dissolve the oil-soluble dye. For example, vinyl chloride, vinyl acetate, styrene, vinylidene chloride, Acrylonitrile, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) butyl acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, glycidyl (meth) phthalate, polyethylene Monomers having one polymerizable unsaturated bond in one molecule such as glycol (meth) acrylate and tetrahydrofurfuryl (meth) acrylate are exemplified.

In the present invention, the monomer composition contains at least 10% by weight of a monomer represented by the general formula (I) (hereinafter, also referred to as a polymerizable monomer (I)). In the above polymerizable monomer (I),: ³ represents a hydrogen atom or a methyl group. Therefore, the polymerizable monomer (I) is an acrylic acid amide derivative or a methacrylic acid amide derivative.

In the polymerizable monomer (I), R ² represents an alkyl group having 3 to 7 carbon atoms. Examples of R ² include an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and a t-butyl group.

The polymerizable monomer (I) has a function of dissolving the dye at a high concentration and causes a cross-linking reaction by heat, so that it gives a thermosetting property to the coating film formed when the colored fine particle emulsion is applied. be able to.

If the content of the polymerizable monomer (I) is less than 10% by weight, it will be difficult to dissolve the dye at a high concentration, and if the colored fine particles are made of a thermosetting resin, crosslinking will not occur. The above range is preferred because it will be sufficient and the solvent resistance and chemical resistance will be insufficient. It is more preferably at least 40% by weight, and even more preferably at least 70% by weight / ₀ .

Examples of the coloring agent usually used in the colored fine particle emulsion include dyes and pigments.

Examples of the above dyes include acid dyes, basic dyes, direct dyes, disperse dyes, and oils. Although a soluble dye or the like can be used, an oil-soluble dye is preferable as the coloring agent used in the present invention because of its high durability and good dispersion in a resin.

As the oil-soluble dye, those having a solubility in an organic solvent at 20 ° C. of 1% by weight or more are preferable. 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 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. More preferably, the content is 10% by weight or less.

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 dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, triphenylmethane dyes, and azo metal complex dyes. Incidentally, in terms of the force color index number, solventblue 44, 45, 59, 1 04; solventred 24 s 68, 8 9, 1 24; solventyellowl 3, 14, 3 3, 7 9, 93; vatb 1 ue 1, 6 vatyell ow 6; These may be used alone or in combination of two or more.

The amount of the oil-soluble dye to be added is preferably 1 to 50 parts by weight based on 100 parts by weight of the monomer composition. When the amount exceeds 50 parts by weight, not only does the concentration of the coloring agent become too high to make it difficult to add, but also the coloring agent may be separated during polymerization. More preferably, it is 5 to 30 parts by weight.

Preferable examples of the coloring agent used in the present invention also include salts obtained by reacting an anionic dye with the cationic monomer represented by the above general formula (II). The cationic monomer represented by the above general formula (II) has relatively strong hydrophobicity, and can precipitate a salt by reacting with the anionic dye.

R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 7 to 12 carbon atoms. Examples of the groups represented by RR ⁵ and R ⁶ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a benzyl group, a cyclohexyl group, and the like. 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 these combinations include a methyl group, a methyl group and a benzyl group, an ethyl group, and an ethyl group. 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 cationic monomer has strong hydrophilicity and is hydrophobic by the reaction with the anionic dye. It is not preferable because it is difficult to form a salt.

The anionic dye is not particularly limited, and examples thereof include an azo dye, an anthraquinone dye, and a triphenyl methane dye.

When a salt obtained by reacting an anionic dye with a cationic monomer represented by the general formula (II) is used as the coloring agent, the cationic monomer is incorporated into the polymer of the colored fine particles. Therefore, the anionic dye is firmly fixed in the colored fine particles by ionic bonding.

When a salt obtained by reacting an anionic dye with the cationic monomer represented by the general formula (II) is used as the coloring agent, the polymerizable monomer is used as the monomer composition. It is preferable to use those containing 90% by weight or more of (I).

When the colored fine particles have a crosslinked structure in the whole fine particles, the monomer composition may use a monomer having two or more vinyl groups in addition to the polymerizable monomer (I). Is preferred.

Examples of the monomer having two or more vinyl groups include, for example, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane triatalylate, pentaerythritol tetraacrylate, aryl methacrylate, and butyl methacrylate. Glyceryl dimethacrylate, dibutylbenzene, triaryl isocyanurate and the like.

The amount of the monomer having two or more vinyl groups is preferably 0.1 to 30% by weight of the total monomer composition. 0.1 weight. If / is less than _0, stiffness is lowered coating film by resulting that coloring fine particles Emarujiyon, may benefit solvent resistance is lowered, if it exceeds 3 0 wt%, decrease the solubility of the coloring material In addition, the aggregation of the emulsion particles and the precipitation of the dye are likely to occur. It is more preferably 0.1 to 10% by weight, still more preferably 0.5 to 10% by weight, particularly Preferably it is 0.5 to 5% by weight.

The colored fine particles preferably have a uniform crosslinked structure on the surface and inside thereof, and the degree of crosslinking is preferably a molecular weight between crosslinks of 5,000 or less. The molecular weight between crosslinks indicates the average molecular weight between crosslink points on a network of a polymer having a crosslinked structure, and is defined by the following formula (1) and is theoretically calculated from the charged amount. It is a numerical value, and the smaller the value, the higher the degree of crosslinking.

∑ (W i X r i) / ∑ (n i X r i) (1)

In the formula, W i is the molecular weight of monomer i which is a constituent of the polymer, ri is the molar ratio of monomer i (∑ ri = l), and ni is the main component contained in one molecule of monomer i. Shows the number of double bonds that can be incorporated into the chain skeleton (however, in the case of a monofunctional monomer, it is calculated as ni = 0). The molecular weight between crosslinks is more preferably 1200 or less.

The colored fine particle emulsion of the present invention can be produced by emulsion polymerization of the above colored composition.

The method for producing the colored fine particle emulsion of the present invention is not particularly limited. For example, a method in which a coloring composition is dispersed in water in the presence of an emulsifier and emulsion polymerization is performed using a water-soluble polymerization initiator; A method of dissolving an oil-soluble polymerization initiator in a composition, dispersing the oil-soluble polymerization initiator in water in the presence of an emulsifier, and then carrying out emulsion polymerization is exemplified. The polymerization initiator is not particularly limited, and examples thereof include oil-soluble or water-soluble organic azo compounds, inorganic peroxides such as potassium persulfate and ammonium persulfate, organic peroxides, inorganic peroxides and sulfites. Redox compositions in combination with reducing agents such as The water-soluble organic azo compounds of ± 1 are classified into cationic compounds and anionic compounds.

Among these polymerization initiators, organic azo compounds are preferable, and organic azo compounds having a 10-hour half-life temperature of 40 to 80 ° C are more preferable.

There is no particular limitation on which organic azo compound is used, but for example, as an oil-soluble dye, an azo metal complex dye, and Z, or obtained by reacting an anionic dye with a cationic monomer. When the resulting salt is used, it is preferable to use an oil-soluble organic azo compound. Coloring with excellent optical properties and durability A fine particle emulsion can be obtained. Further, an optimum one may be selected according to the emulsifier described below.

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. If the amount is less than 0.1 part by weight, the polymerization reaction may not proceed smoothly. If the amount exceeds 10 parts by weight, the molecular weight of the obtained vinyl resin may be too low. The emulsifier, more preferably 0.2 to 5 parts by weight, is not particularly limited, and examples thereof include anionic, cationic, and nonionic surfactants. Of these, anionic surfactants are preferred. Cationic surfactants are not very dispersible, and nonionic surfactants tend to increase the particle size of the resulting emulsion.

Examples of the anionic surfactant include alkyl sulfates such as sodium alkyl sulfate and ammonium sulfate, and alkyl sulfonates such as sodium alkyl sulfonate and ammonium sulfonate. Of these, alkyl sulfonates are preferred because they have the advantage of not adversely affecting the physical properties of the coating film.

Further, an anionic surfactant having a polymerizable group can be used as the anionic surfactant. As the anionic surfactant having a polymerizable group,

Examples thereof include a sulfonic acid (salt) type, a carboxylic acid (salt) type, and a phosphate ester (type). Among these, phosphate esters having a polymerizable unsaturated bond are

Since it is fixed to the emulsion fine particles, it is preferable because it has an advantage that the physical properties of the coating film are not adversely affected.

The above emulsifiers may be used alone or in combination of two or more.

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.

The concentration of the emulsifier is not particularly limited, but is preferably 0.5 to 10% by weight in the polymerization system. Although the amount of the emulsifier is not particularly limited, the weight ratio of the colored composition to the aqueous solution of the emulsifier (colored composition / aqueous solution of the emulsifier) It is preferably 1/5-1/1.

The reaction temperature of the above emulsion polymerization is not particularly limited, but is usually preferably from 10 to 10 ° C. More preferably, it is 40 to 80 ° C.

The reaction conditions for producing the colored fine particle emulsion by the emulsion polymerization are not particularly limited, and may be set according to the types of the coloring composition, the polymerization initiator, and the emulsifier used. For example, a coloring composition, an emulsifier, and deionized water are charged into a flask, the temperature is raised to the reaction temperature while stirring under a nitrogen stream, and then the polymerization initiator is injected into the flask, and the oil The coloring composition of the present invention is obtained by dropping the coloring composition containing the dye over 1 to 2 hours, further stirring at the same temperature for 3 to 4 hours, and then performing emulsion polymerization using a method of cooling to room temperature. Emulsion can be manufactured.

In addition, the coloring composition is dispersed in water in the presence of an emulsifier, and a polymerization initiator is added to obtain a dispersion of seed particles in advance. The colored fine particle emulsion of the present invention can also be obtained by the method of side polymerization in which a dispersion obtained by dispersing a mixture with an emulsifier in water in the presence of an emulsifier is gradually dropped. When introducing a cross-linking structure only on the surface of the colored fine particles, or when forming a bias in the cross-linking density between the surface of the colored fine particles and the inside, that is, when the cross-linking on the surface of the colored fine particles is made denser than the inside, By crosslinking the surface of the previously prepared fine particles. Hereinafter, such colored fine particles in which the cross-linking on the surface of the fine particles is denser than the internal cross-linking are referred to as surface cross-linked colored fine particles.

Examples of the method for producing the surface crosslinked colored fine particles include, for example, fine particles obtained by polymerizing a monomer composition containing a monomer having a functional group capable of reacting with a crosslinking agent and a colored composition comprising a coloring agent. And a method of reacting a crosslinking agent.

Examples of the monomer having a functional group capable of reacting with the crosslinking agent include a monomer containing an epoxy group such as glycidyl (meth) acrylate and a monomer containing an isocyanate group such as 2-methacryloyloxyethyl isocyanate. Monomer, hydroxyl-containing monomer such as hydroxysethyl (meth) acrylate, carboxyl group such as (meth) acrylic acid Monomer, a primary or secondary amino group-containing monomer, and the like.

As the crosslinking agent, a compound having two or more functional groups capable of reacting with the functional group contained in the monomer is used.

Examples of such compounds include polyfunctional amine compounds having an amino group such as ethylenediamine, 1,2-propanediamine, 1,3-propanediamine and diethylenetriamine; and polyfunctional amine compounds having a hydroxyl group such as ethylenedalicol and glycerin. Polycarboxylic acid compounds having a carboxylic acid such as succinic acid, adipic acid, and maleic acid; acid anhydrides such as maleic anhydride and phthalic anhydride; polyfunctional isocyanate compounds, and polyfunctional epoxy compounds. No.

The amount of the crosslinking agent to be added is determined by the relationship between the amount of the functional group in the crosslinking agent and the amount of the functional group capable of reacting with the crosslinking agent in the fine particles. It is preferable that If the former exceeds the equivalent of the latter, a plurality of functional groups of the cross-linking agent cannot react and the cross-linking point is sealed, so that the cross-linking effect cannot be sufficiently obtained, which is not preferable. In particular, in order for the crosslinking agent to sufficiently participate in a functional group on the surface of the fine particles which is easily reacted, crosslinking is preferably performed in such a ratio.

As described above, in the method of crosslinking the surface of the previously prepared fine particles with a crosslinking agent and introducing a desired crosslinking structure, the degree of crosslinking is represented by the molecular weight between bridges defined by the following formula (2). It is preferable that the intermolecular weight is 500 or less. More preferably, it is 400 or less.

∑ (W i X ri) / (∑ ni X ri + ∑ mi X ri) (2) where W i is the molecular weight of monomer i as a constituent, and ri is the molar ratio of monomer i (∑ ri = l), ni is the number of double bonds that can be incorporated into the main chain skeleton contained in one molecule of monomer i (however, in the case of a monofunctional monomer, it is calculated as ni = 0), mi Represents the number of functional groups that form a crosslinking point by reacting with a crosslinking agent contained in one molecule of the monomer i. In this case, the molecular weight between the functional groups of the cross-linking agent is ignored as approximately zero.

Even if there are functional groups capable of reacting with the cross-linking agent on the surface of the fine particles, if the total number of functional groups that can serve as cross-linking points is smaller than the total number of functional groups in the cross-linking agent, the shortage of the functional groups will be Must be considered so as not to be estimated.

Other methods for producing the surface-crosslinked colored fine particles include, for example, a monomer composition and After the monomer having two or more vinyl groups and the oil-soluble polymerization initiator are absorbed in fine particles obtained by polymerizing a coloring composition comprising a coloring agent, the monomer having two or more vinyl groups is absorbed. Is polymerized.

As the monomer having two or more vinyl groups, the same one as described above is used.

The compounding amount of the monomer having two or more vinyl groups is preferably 1 to 20% by weight based on all the monomers. When the amount is less than 1% by weight, it becomes difficult to produce colored resin particles having excellent mechanical properties. On the other hand, when the amount exceeds 20% by weight, the fine particles of the raw material become unstable.

As the oil-soluble polymerization initiators, for example, base peroxide Nzoiru, 3, 5, 5-preparative to Rimechinore hexa Noi Honoré Per O key side, t Buchi Paokishi into single 2-Echinore key Sanoeto, di _t one Buchirupao Organic peroxides such as oxides; organic azo compounds such as azobisisobutyronitrile, azobiscyclohexacarbonitrile, and azobis (2,3-dimethylvaleronitrile).

In the process of absorbing the monomer having two or more vinyl groups and the oil-soluble polymerization initiator into the emulsion composed of the fine particles, the monomer having two or more vinyl groups and the oil-soluble polymerization initiator are usually dissolved in water. This is performed by finely dispersing with stirring and stirring with the fine particles for 1 to 24 hours.

The polymerization temperature of the monomer having two or more vinyl groups absorbed is selected according to the polymerization initiator, but is usually in the range of 2 to 100 ° C., and more preferably 40 to 100 ° C. It is in the range of 90 ° C.

In order to obtain a colored fine particle emulsion having excellent mechanical stability, in addition to the above-mentioned crosslinking, colored fine particles in which a resin having a glass transition point of a homopolymer of 50 ° C. or more is formed at least in the surface layer are preferable. . When the glass transition point of the homopolymer is less than 50 ° C., the colored fine particles tend to coalesce during ink jet printing.

Monomers having a glass transition point of 50 ° C or higher of the homopolymer include, for example, butyl chloride, butyl acetate, styrene, vinylidene chloride, acrylonitrile, methyl methacrylate, methyl methacrylate, methacrylic acid. T-butyl, cyclohexyl methacrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) ) Polymerizable monomers having one polymerizable unsaturated bond in one molecule such as acrylate.

To express redissolvability the colored particles Emarujon of the present invention, the monomer composition, a vinyl monomer containing an epoxy group and is a 1-6 0 wt ° / ₀ containing child preferred .

The above-mentioned resolubility means that when the coating film is immersed in an aqueous medium, the coating film is easily dissociated to such an extent that the shape of the coating film does not remain. Specifically, it is preferable that 95% or more of the portion of the coating film immersed in water left to dry at room temperature becomes a coating film piece having a size (longest diameter) of 100 / m or less. If the size (longest diameter) of the coating film exceeds 100 μπι exceeds 5%, resolubility will be lost and clogging of the nozzle hole will occur.

By introducing an epoxy group into the colored fine particles, the colored fine particle emulsion of the present invention can be applied to a substrate and left to dry at room temperature to give a coating film having resolubility in an aqueous medium. .

The above-mentioned drying at room temperature means that the colored fine particle emulsion is applied to a substrate and then dried without applying a temperature higher than room temperature. Specifically, it is preferable to dry in an environment of a temperature of 5 to 38 and a humidity of 30 to 95% for 5 minutes to 1000 hours. If the time is less than 5 minutes, it cannot be said that the film is re-dissolved because a coating film is not formed, and if the time exceeds 1000 hours, factors other than drying, such as resin crosslinking and decomposition, are added. More preferably, it is dried at a temperature of 5 to 38 and a humidity of 30 to 95% for 10 minutes to 100 hours.

The epoxy group-containing vinyl monomer is not particularly limited as long as it contains a polymerizable unsaturated bond and an epoxy group in the molecule. Specifically, glycidyl methacrylate is preferably used because of its compatibility with the polymerizable monomer (I), the solubility of the oil-soluble dye, and the adhesion to the base material.

When the content of the above-mentioned vinyl monomer having an epoxy group is less than 1% by weight, the effect of improving the adhesion of the coating film obtained by the colored fine particle emulsion to the substrate is hardly recognized, and 60% by weight When the ratio exceeds the above range, it may be difficult to polymerize colored fine particles containing a colorant having a preferable particle size.

As a vinyl monomer for exhibiting redispersibility in the dried colored fine particle emulsion, those capable of taking an ionic structure in an aqueous solvent can also be suitably used. like this Suitable vinyl monomers include, for example, bierpyridine acrylic acid, methacrylic acid, maleic acid, maleic anhydride, dimethylaminoethyl acrylate, getylaminoethyl atalinoleate, acrylamide t-butyl sulfonic acid, 3-dimethyl Ethyl luminoacrylate, itaconic acid, pentadecylenic acid, crotonic acid, citraconic acid, N_ [3- (dimethylamino) propyl] acrylamide and the like. Of these, vinyl pyridine is the most suitable in terms of affinity with the dye.

When such a colored fine particle emulsion having resolubility in water is used as an ink for ink jet printing, since it has resolubility in water as a solvent as described above, it is aggregated around the nozzle hole and in the flow path. No matter is formed, and even if agglomerates are formed, they are quickly washed away due to re-dissolving property, so that there is no clogging of the nozzles and the discharge property is good.

By introducing an epoxy group into the colored fine particles and further containing an amine-based silane coupling agent, the colored fine particle emulsion of the present invention has good adhesion to glass and metal.

The amine silane coupling agent is not particularly limited as long as it is a silane compound having an amino group in the molecule. Preferably, an alkoxysilane having a total carbon number of 30 or less in one molecule and having a carbon number of 10 or less that functions as a silane coupling agent is used. When the total number of carbon atoms exceeds 30, dispersibility in the colored fine particle emulsion may be deteriorated. When the number of carbon atoms of the alkoxide on the silicon atom exceeds 10, the substitution reaction on the silicon atom proceeds. May be difficult.

Examples of the amine-based silane coupling agent include N— / 3 (aminoethyl) aminopropylmethyldimethoxysilane, N— / 3 (aminoethyl) _Ί— Rinominovirtrimethoxysilane, Ν—β (aminoethyl ) Gamma-aminopropyltriethoxysilane, phenyl- _y -aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, -aminopropyltrimethoxysilane and the like. These may be used alone or in combination of two or more.

The content of the amine-based silane coupling agent is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the solid content of the colored fine particle emulsion of the present invention. New If it is less than 0.01 part by weight, there is no effect of addition, and if it exceeds 10 parts by weight, it is too much and does not mix with the colored fine particle emulsion or the stability of the colored fine particle emulsion is impaired. May aggregate.

The method for adding the amine-based silane coupling agent to the colored fine particle emulsion of the present invention is not particularly limited. For example, a method in which the amine-based silane coupling agent is added to an aqueous medium before polymerization of the colored fine particles; And a method of adding it to the colored fine particle emulsion.

An ink jet printing ink can be prepared by adding a humectant to the colored fine particle emulsion of the present invention.

The humectant is preferably a water-soluble organic compound having a boiling point of 10 ° C. or more, for example, glycerin, ethylene glycol, and diethylene glycol.

Triethylene glycol monoethylene glycol ethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, dimethyl sulfoxide, pyrrolidone and its derivatives, alcohol, etc. Can be

The concentration of the humectant is preferably 5 to 40% by weight in the ink for ink jet printing. The solid content concentration of the colored fine particles in the ink for inkjet printing is preferably 3 to 20% by weight.

An ink jet printing ink containing the colored fine particle emulsion of the present invention and a humectant is also one of the present invention.

The ink jet printing ink having the three primary colors of red, green, and blue or the complementary colors of cyan, magenta, and yellow is printed on a glass substrate or a resin substrate of a liquid crystal display panel by an ink jet method to form a color filter for a liquid crystal display. Can be made.

By adding an electrolyte to the colored fine particle emulsion of the present invention, a colored fine particle emulsion for an electrodeposition color filter can be obtained.

The electrolyte is not particularly limited as long as it is a water-soluble salt. Inorganic salts such as lithium, potassium chloride, ammonium chloride and ammonium perchlorate; alkyl sulfates such as sodium alkyl sulfate and ammonium sulfate; and anions such as alkyl sulfonates such as sodium alkyl sulfonate and ammonium sulfonate. And a cationic surfactant such as an aliphatic amine salt, a benzalkonium salt, a pyridinium salt, and an imidazolinium salt. The concentration of the electrolyte is preferably 0.5 to 5% by weight in the colored fine particle emulsion for the electrodeposition color filter. When the amount is less than 0.5% by weight, the obtained colored resin emulsion has poor electrodeposition properties, and a high voltage may be required for electrodeposition. On the other hand, when the amount exceeds 5% by weight, the obtained colored resin emulsion is obtained. In some cases, the moisture resistance and water resistance of the coating film may decrease.

The solid concentration of the colored fine particles in the colored fine particle emulsion for the electrodeposition color filter is preferably 5 to 50% by weight.

Electrodeposition color having three primary colors of red, green, and blue or complementary colors of cyan, magenta, and yellow One-filter colored fine particles Emulsion For liquid crystal display panels with transparent electrodes such as ITO formed by electrodeposition using an ink An electrodeposited color filter can be made by forming a color filter layer on a glass substrate or resin substrate.

As a method for producing the above-mentioned electrodeposited color filter, a substrate for a liquid crystal display panel on which a transparent electrode is formed and a counter electrode are immersed in a colored fine particle emulsion for an electrodeposited color filter, and an electric field is applied. It is formed.

The applied potential is preferably 5 to 50 V, and the applied time is preferably 3 to 60 seconds. The thickness of the formed color filter layer is preferably 0.3 to 3; χιη.

The pattern of the electrodeposited color filter may be controlled by an electrode pattern, or an insulating layer may be formed by a photolithographic method or the like on a liquid crystal display panel substrate on which a transparent electrode having no pattern is formed. The electrodeposited color filter may be patterned, and then the insulating layer may be removed.

By performing a heat treatment after the formation of the electrodeposited color filter, a crosslinking reaction by the polymerizable monomer (I) progresses, and the solvent resistance can be increased. Heat treatment conditions and Preferably, the temperature is 120 to 250 ° C., and the time is 10 to 60 minutes. The colored fine particle emulsion for an electrodeposition color filter is also one of the present invention.

By removing the aqueous medium in the colored fine particle emulsion of the present invention, the colored fine particles can be separated. As a method for removing the aqueous medium, a spray-dry method or a freeze-dry method in which coalescence of fine particles is small is preferable.

After the colored fine particles are separated from the colored fine particle emulsion of the present invention and dried, the colored fine particles may be subjected to crushing or the like.

The colored fine particles obtained from the above-mentioned colored fine particle emulsion are also one of the present invention. 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 only these Examples. Example 1

Charge 2 parts by weight of sodium dodecyl sulfate, 198 parts by weight of deionized water, and 5 parts by weight of n-butoxymethylacrylamide into a flask, and stir the mixture at 50 ° C while stirring under a nitrogen stream. Raised to. Next, 5 parts by weight of an ethanol solution containing 0.5 parts by weight of V-70 (oil-soluble azo-based polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) was injected into the flask, and immediately the following composition was obtained. The aqueous dispersion of the coloring composition was dropped over 2 hours. Then, after stirring at the same temperature for 3 hours, the mixture was cooled to room temperature to obtain a colored fine particle emulsion.

The obtained colored fine particle emulsion was filtered with a filter having a pore size of 1 m, and the particle size of the colored fine particles was measured using a laser light scattering particle size distribution analyzer (device name: Microtrack, manufactured by Nikkiso Co., Ltd.). However, the average particle size was 14.5 nm. The molecular weight between crosslinks calculated from the composition was 28766

(Coloring composition) n-butoxymethyl acrylamide (molecular weight: 157): 45 parts by weight (0.287 mol part: ratio 0.355)

Methyl methacrylate (molecular weight: 100): 50 parts by weight (0.500 mole parts: ratio 0.620)

FANCRYL FA-73 1 A (Hitachi Chemical Industries, Ltd. Tris (2-hydroxyethyl) acrylate of isocyanuric acid, trifunctional monomer: molecular weight 423): 5 parts by weight (0.012 mol part: ratio 0 . 0 1 5)

Orazol Red G (Ciba Specialty Chemicals, metal complex of red azo dye): 30 parts by weight

V—65 (molecular weight 248): 2 parts by weight (0.008 mol part: ratio 0.010)

(Dispersion medium)

Deionized water: 100 parts by weight

Neugen EA 170 (Nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 6 parts by weight A dispersion medium was added to the coloring composition under stirring to obtain an aqueous dispersion of the coloring composition. Example 2

An emulsion was prepared in the same manner except that the composition of the coloring composition used in Example 1 was changed to the composition shown below. The average particle size of the fine particles of the emulsion thus obtained was 21 O nm.

The molecular weight between cross-links of the fine particle surface calculated from the composition was 959.

(Coloring composition)

n-butoxymethyl acrylamide (molecular weight: 157): 40 parts by weight (0.255 mol part: ratio 0.341)

Methyl methacrylate (molecular weight: 100): 45 parts by weight (0.450 mol: ratio 0.601)

Fancryl FA-73 1 A (tris (2-hydroxyche) manufactured by Hitachi Chemical Co., Ltd. Cyl) Acrylic acid ester of isocyanuric acid, trifunctional monomer: molecular weight 423): 15 parts by weight (0.035 mol part: ratio 0.047)

Orazol Red G (Metal complex of red azo dye, manufactured by Ciba Specialty Chemicals): 30 parts by weight

V—65 (molecular weight: 248): 2 parts by weight (0.008 mole part: ratio: 0.001 1)

(Dispersion medium)

Deionized water: 100 parts by weight

Neugen EA170 (Nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 6 parts by weight A dispersion medium was added to the coloring composition under stirring to obtain an aqueous dispersion of the coloring composition. Example 3

An emulsion was prepared in the same manner except that the composition of the coloring composition used in Example 1 was changed to the composition shown below. The average particle size of the fine particles of the emulsion thus obtained was 107 nm.

Next, while stirring the obtained emulsion at room temperature, 13.0 parts by weight of a 5% by weight aqueous solution of 1,2-propanediamine was slowly added slowly to perform a bridging treatment on the surface of the fine particles. . It is considered that the glycidyl groups on the surface of the fine particles were all crosslinked and a crosslinked structure was formed by this operation.

The molecular weight between fine particle surfaces crosslinked calculated from the composition was 1787.

(Coloring composition)

n-Butoxymethyl acrylamide (molecular weight: 157): 45 parts by weight (0.287 monole: ratio: 0.355)

Methyl methacrylate (molecular weight: 100): 45 parts by weight (0.450 mol: ratio 0.558)

Glycidyl methacrylate (molecular weight 142): 5 parts by weight (0.035 mol part: ratio 0.044) Orazo Red G (Ciba Specialty Chemicals, metal complex of red azo dye): 30 parts by weight

V—65 (molecular weight 248): 2 parts by weight (0.008 mol part: ratio 0.010)

(Dispersion medium)

Deionized water: 100 parts by weight

Neugen EA 170. (Nonionic surfactant, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.): 6 parts by weight A dispersion medium was added to the coloring composition under stirring to obtain an aqueous dispersion of the coloring composition. Example 4

An emulsion was prepared in the same manner except that the composition of the coloring composition used in Example 1 was changed to the composition shown below. The average particle size of the fine particles of the emulsion thus obtained was 112 nm.

The molecular weight between crosslinks of the fine particle surface calculated from the composition was 1190.

(Coloring composition)

n-butoxymethyl acrylamide (molecular weight: 157): 45 parts by weight (0.287 monolithic part: ratio 0.356)

Methyl methacrylate (Molecular weight 100): 45 parts by weight (0.450 mol parts: ratio 0.559)

Glycidyl methacrylate (molecular weight: 142): 5 parts by weight (0.035 mol part: ratio 0.044)

Dibutyl adipate (bifunctional monomer: molecular weight 198): 5 parts by weight (0.025 mol part: ratio 0.03 1) Orazol Red G (manufactured by Ciba Specialty Chemicals, metal complex of red azo dye): 30 parts by weight

V-65 (molecular weight: 248): 2 parts by weight (0.008 mol part: ratio: 0.010) (dispersion medium)

Deionized water: 100 parts by weight

Neugen EA 170 (Nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 6 parts by weight A dispersion medium was added to the coloring composition under stirring to obtain an aqueous dispersion of the coloring composition. Example 5

An emulsion was prepared in the same manner except that the composition of the coloring composition used in Example 1 was changed to the composition shown below. The average particle size of the fine particles of the emulsion thus obtained was 120 nm.

Next, while stirring the obtained emulsion at room temperature, 26.0 parts by weight of a 5% by weight aqueous solution of 1,2-propanediamine was slowly added slowly to perform a bridging treatment on the surface of the fine particles. It is considered that the glycidyl groups on the surface of the fine particles were all crosslinked and a crosslinked structure was formed by this operation.

The molecular weight between fine particle surface crosslinks calculated from the composition was 1092.

(Coloring composition)

n-butoxymethylacrylamide (molecular weight: 157): 40 parts by weight (0.255 mol part: ratio 0.32 1)

Methyl methacrylate (molecular weight: 100): 45 parts by weight (0.450 mol parts: ratio 0.567)

Glycidyl methacrylate (molecular weight: 142): 10 parts by weight (0.070 mol part: ratio 0.089)

Dibutyl adipate (bifunctional monomer: molecular weight 198): 2 parts by weight (0.010 mol part: ratio 0.013) Orazo Red G (metal complex of red azo dye, manufactured by Ciba Specialty Chemicals): 30 parts by weight

V—65 (molecular weight: 248): 2 parts by weight (0.008 mole part: ratio: 0.010) (dispersion medium)

Deionized water: 100 parts by weight

Neugen EA 170 (Nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 6 parts by weight A dispersion medium was added to the coloring composition under stirring to obtain an aqueous dispersion of the coloring composition. Example 6

An emulsion was prepared in the same manner except that the composition of the coloring composition used in Example 1 was changed to the composition shown below. The average particle size of the fine particles of the emulsion thus obtained was 106 nm.

Next, 26.0 parts by weight of a 5% by weight aqueous solution of 1,2-propanediamine was slowly added slowly to the obtained emulsion while stirring at room temperature to carry out a bridging treatment on the surface of the fine particles. It is considered that the glycidyl groups on the surface of the fine particles were all crosslinked and a crosslinked structure was formed by this operation.

In addition, the molecular weight between fine particle surfaces crosslinked calculated from the composition was 1377.

(Coloring composition)

n-butoxymethyl acrylamide (molecular weight: 157): 40 parts by weight (0.255 mol part: ratio 0.325)

Methyl methacrylate (molecular weight: 100): 45 parts by weight (0.450 mol parts: ratio 0.575)

Glycidyl methacrylate (molecular weight: 142): 10 parts by weight (0.070 mol part: ratio 0.090)

Orazole Red G (Metal complex of red azo dye, manufactured by Ciba Specialty Chemicals): 30 parts by weight V-65 (molecular weight 248): 2 parts by weight (0.008 mole part: ratio 0.010)

(Dispersion medium)

Deionized water: 100 parts by weight

Neugen EA170 (Nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 6 parts by weight A dispersion medium was added to the above colored composition with stirring to obtain an aqueous dispersion of the colored composition. Example 7

2 parts by weight of sodium dodecyl sulfate, 504 parts by weight of New Frontier S, 194 parts by weight of deionized water, and 10 parts by weight of n-butoxymethyl acrylamide are charged into a flask and stirred under a nitrogen stream. Meanwhile, the liquid temperature was raised to 50 ° C. Next, 10 parts by weight of an ethanol solution containing 0.5 parts by weight of V-70 (oil-soluble azo-based polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) was poured into the flask, and immediately, the following composition was used. A colored composition having the following was dropped over 2 hours. Then, after stirring at the same temperature for 3 hours, the mixture was cooled to room temperature to obtain a fine emulsion.

V-65 (oil-soluble azo-based polymerization initiator, manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 30 parts by weight of ion-exchanged water, 5 parts by weight of trimethylolpropane triatalylate, and 1 part by weight of ethanol 0.1 Weight part and 0.3 part by weight of sodium dodecyl sulfate were added and emulsified with a homogenizer. The obtained emulsion was added to 100 parts by weight of the emulsion of the fine particles, and the mixture was stirred at 25 ° C. and 200 rpm for 3 hours to absorb the trimethylol-pulp pantria triarylate into the fine particles in the emulsion. Was. The temperature of the emulsion was raised to 50 ° C., and the mixture was reacted for 8 hours with stirring under nitrogen to obtain a colored fine particle emulsion having a trimethylolpropane triacrylate polymer on the surface.

The obtained colored fine particle emulsion was filtered through a filter having a pore size of 1 m, and the particle size of the colored fine particles was measured using a laser light scattering particle size distribution analyzer (device name: Microtrack, manufactured by Nikkiso Co., Ltd.). However, the average particle size was 132 nm. (Coloring composition)

n-butoxymethyl acrylamide: 89 parts by weight

Ethylene glycol dimethacrylate (bifunctional monomer): 1 part by weight Orazo-Ilred G (manufactured by Ciba Specialty Chemicals, metal complex of red azo dye): 20 parts by weight

The synthesis was carried out in the same manner as in Example 7 except that 5 parts by weight of fancryl FA-731A (manufactured by Hitachi Chemical Co., Ltd.) was used instead of trimethylolpropane triatalylate, and a cross-linking component To obtain a colored fine particle emulsion.

The resulting colored fine particle emulsion was filtered through a filter having a pore size of 1; / πι, and the particle size of the colored fine particles was measured. The average particle size was 120 nm. Example 9

2 parts by weight of sodium dodecyl sulfate, 504 parts by weight of New Frontier S, 194 parts by weight of deionized water, and 10 parts by weight of n-butoxymethyl acrylamide are charged into a flask and stirred under a nitrogen stream. Meanwhile, the liquid temperature was raised to 50 ° C. Next, 10 parts by weight of an ethanol solution containing 0.5 part by weight of V-70 (oil-soluble azo-based polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) was poured into the flask, and immediately, the following composition The dye solution was added dropwise over 2 hours, and then stirred at the same temperature for 3 hours, and then cooled to room temperature to obtain resin fine particle-containing emulsion (hereinafter referred to as emulsion A).

(Composition of dye solution)

n-butoxymethyl acrylamide 8 9 parts by weight

1 part by weight of ethylene glycol dimethacrylate

Orazo Irretsu KG (Ciba Specialty 'Chemicals, metal complex of red azo dye) 20 parts by weight Next, V-65 (Wako Pure Chemical Industries, oil-soluble azo-based polymerization initiator) dissolved in 30 parts by weight of ion-exchanged water, 5 parts by weight of methyl methacrylate, and 1 part by weight of ethanol 0.1 part by weight And 0.3 parts by weight of sodium dodecyl sulfate, and emulsified with a homogenizer.

25. The obtained emulsion was added to 100 parts by weight of emulsion A. The monomer and the polymerization initiator were absorbed by the resin fine particles in the emulsion A by stirring at 200 ° C. for 3 hours at a temperature of C.

Next, this dispersion was heated to 50 ° C., and a polymerization reaction was carried out for 8 hours while stirring under a nitrogen atmosphere to obtain a colored resin emulsion having poly (methyl methacrylate) on the surface. Comparative Example 1

A colored fine particle emulsion was prepared in the same manner as in Example 1 except that the composition of the coloring composition used was changed to the composition shown below. The average particle size of the colored fine particles of the emulsion thus obtained was 95 nm.

In Comparative Example 1, the fine particles were not crosslinked.

(Coloring composition)

n-butoxymethyl acrylamide (molecular weight: 157): 45 parts by weight (0.287 mol part: ratio 0.357)

Methyl methacrylate (molecular weight: 100): 50 parts by weight (0.500 mole parts: ratio 0.623)

Orazol Red G (manufactured by Ciba Specialty Chemicals, metal complex of red azo dye): 30 parts by weight

V—65 (molecular weight 248): 2 parts by weight (0.008 mole part: ratio 0.010)

(Dispersion medium)

Deionized water: 100 parts by weight

Neugen EA 170 (Daiichi Kogyo Seiyaku Co., Ltd., nonionic surfactant): 6 parts by weight A dispersion medium was added to the coloring composition under stirring to obtain an aqueous dispersion of the coloring composition. Comparative Example 2

The emulsion used in Example 3 was used for evaluation without adding 1,2-propanediamine.

In this emulsion, no crosslinked structure was formed on the particle surface.

[Evaluation]

The colored fine particle emulsions obtained in Examples 1 to 9 and Comparative Examples 1 and 2 were used as inks for ink jet printing with the following composition, and a piezo ink jet printer (trade name: PM-7500C, manufactured by Seiko Epson Corporation) The print test was performed in). The results are shown in Table 1. (Composition of evaluation ink)

Colored fine particle emulsion: 25 parts by weight

Glycerin: 25 parts by weight

Ion-exchanged water: Add the necessary amount so that the solid content of the colored fine particle emulsion becomes 10% by weight.

The printing stability and the ink straightness evaluation in Table 1 were evaluated based on the following criteria. Printing stability 〇: A410 sheets can be printed stably.

Δ: Clogging of the nozzle occurs when A4 is 2 or more and 10 or less. X: Nozzle clogging occurs with two or less A4 sheets.

Ink straightness 〇: Ink is ejected from the nozzle in a downward direction

X: Ink is ejected obliquely from the nozzle. Example 10

Charge 1 part by weight of sodium dodecyl sulfate, 97 parts by weight of ion-exchanged water, and 5 parts by weight of n-butoxymethylacrylamide into a flask, and bring the temperature to 50 ° C while stirring under a nitrogen stream. Raised. Next, 2.5 parts by weight of an ethanol solution containing 0.25 parts by weight of an oil-soluble azo polymerization initiator (trade name “V-70” manufactured by Wako Pure Chemical Industries, Ltd.) was injected into the flask. Immediately, an aqueous dispersion of a dye solution having the composition shown in Table 2 below was dropped at the same temperature over 3 hours. Thereafter, the mixture was stirred at the same temperature for 3 hours, and then cooled to room temperature to obtain a colored resin fine particle emulsion. Table 2

Example 1 1

An emulsion was prepared in the same manner as in Example 10 except that the composition of the dye solution used in Example 10 was changed to the composition shown in Table 2 above. Example 1 2

An emulsion was prepared in the same manner as in Example 10 except that the composition of the dye solution used in Example 10 was changed to the composition shown in Table 2 above. Comparative Example 3

The following aqueous dispersion was charged into a flask, and the liquid temperature was raised to 50 ° C while stirring under a nitrogen stream. Next, 2.5 parts by weight of an ethanol solution containing 0.25 parts by weight of V-70 (oil-soluble azo-based polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) was injected into the flask, and immediately, The dye solution of the composition was added dropwise over 2 hours. Then, after stirring at the same temperature for 3 hours, the mixture was cooled to room temperature to obtain a colored fine particle emulsion.

(Water dispersion)

Sodium dodecyl sulfate Ion exchange water: 97 parts by weight

n-Butoxymethylacrylamide: 5 parts by weight

(Dye solution)

Tetrahydrofurfurinoacrylate: 45 parts by weight

Orazol Red G (Ciba Specialty Chemicals, metal complex of red azo dye): 12.5 parts by weight

Ion exchange water: 50 parts by weight

Sodium dodecyl sulfate: 0.5 parts by weight

V-65 (Wako Pure Chemical Industries, Ltd., oil-soluble azo polymerization initiator): 1 part by weight The obtained colored fine particle emulsion was filtered with a filter having a pore size of 1 μm to obtain laser light scattering particles. When the particle size of the colored fine particles was measured using a diameter distribution measuring device (device name: Microtrack, manufactured by Nikkiso Co., Ltd.), the average particle size was _{122 nm} . Comparative Example 4

(Water dispersion)

Sodium dodecyl sulfate: 1 part by weight

Ion exchange water: 97 parts by weight

n-butoxymethyl acrylamide: 5 parts by weight

(Dye solution)

Methyl methacrylate: 22 parts by weight Acrylonitrile: 23 parts by weight

Orazole Red G (Metal complex of red azo dye, manufactured by Ciba Specialty Chemicals): 12.5 parts by weight

Ion exchange water: 50 parts by weight

Sodium dodecyl sulfate: 0.5 parts by weight

V-65 (Wako Pure Chemical Industries, Ltd., oil-soluble azo-based polymerization initiator): 1 part by weight The obtained colored fine particle emulsion is filtered through a filter having a pore size of 1 / xm to obtain laser light scattering particles. The average particle diameter was 78 nm when the particle diameter of the colored fine particles was measured using a diameter distribution measuring device (apparatus name: Microtrack, manufactured by Nikkiso Co., Ltd.). Comparative Example 5

An emulsion was prepared in the same manner as in Example 10 except that the composition of the dye solution used in Example 10 was changed to the composition shown in Table 2 above.

(Evaluation of resolubility)

After applying the colored fine particle emulsion obtained in Examples 10 to 12 and Comparative Examples 3 to 5 to a glass plate of 100 mm × 10 Omm, 23. C, left in a 65% humidity environment for 30 minutes to dry. The obtained coating film was immersed in water together with the glass plate, and after 5 minutes, the glass plate was taken out of the water. The glass plate was shaken a few times when it was taken out. The remaining water was filtered through a stainless wire mesh having a mesh size of 90 / zm in Examples and 106 / m in Comparative Examples, and the ratio of the weight of the coating film remaining on the wire mesh to the total coating weight was measured. Table 3 shows the results.

The colored fine particle emulsions obtained in Examples 10 to 12 and Comparative Examples 3 to 5 were used as ink jet printing inks by the following formulation, and a piezo ink jet printer (trade name: PM-750C, Seiko) (Epson) to perform a print test on A4 size paper. Table 3 also shows the results.

(Composition of evaluation ink) Colored fine particle emulsion: 25 parts by weight

Glycerin: 25 parts by weight

Ion-exchanged water: Add the necessary amount so that the solid content of the colored fine particle emulsion becomes 10% by weight. Table 3

The printing stability and the straightness of the ink in Table 3 were evaluated based on the following criteria. Printing stability 〇: A410 sheets can be printed stably.

Ink straightness 〇: Ink is ejected from the nozzle in a downward direction

X: Ink is ejected obliquely from the nozzle. Example 13

The following aqueous dispersion was charged into a flask, and the liquid temperature was raised to 5 while stirring under a nitrogen stream. Next, 2.5 parts by weight of an ethanol solution containing 0.25 parts by weight of V-70 (oil-soluble azo-based polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) was injected into the flask, and immediately, The dye solution of the composition was added dropwise over 2 hours. Then, after stirring at the same temperature for 3 hours, the mixture was cooled to room temperature to obtain colored fine particle emulsion B.

(Water dispersion)

Sodium dodecyl sulfate: 1 part by weight Ion exchange water: 97 parts by weight

n-butoxymethylacrylamide: 5 parts by weight

(Dye solution)

n-butoxymethyl acrylamide: 17 parts by weight

Glycidyl methacrylate: 23 parts by weight

Isobonyl acrylate: 4 parts by weight

Dibutyl adipate: 1 part by weight

Orazol Red G (manufactured by Ciba Chemical Corporation, metal complex of red azo dye): 12.5 parts by weight

Ion exchange water: 50 parts by weight

Sodium dodecyl sulfate: 0.5 parts by weight

V-65 (Wako Pure Chemical Industries, oil-soluble azo polymerization initiator): 1 part by weight N- / 3 (aminoethyl) γ- based on 100 parts by weight of the obtained colored fine particle emulsion B 0.2 parts by weight of aminopropyl trimethoxysilane was diluted with 10 times the amount of ion-exchanged water, and added with stirring at room temperature to obtain a colored fine particle emulsion. The obtained colored fine particle emulsion was filtered through a filter having a pore size of 1 μm, and the particle size of the colored fine particles was measured using a laser light scattering particle size distribution analyzer (device name: Microtrack, manufactured by Nikkiso Co., Ltd.). However, the average particle size was 92 nm. Example 14

Charge 1 part by weight of sodium dodecyl sulfate, 97 parts by weight of ion-exchanged water, and 5 parts by weight of n-butoxymethylacrylamide into a flask, and stir the mixture at 50 ° C while stirring under a nitrogen stream. Raised. Next, 2.5 parts by weight of an ethanol solution containing 0.25 parts by weight of V-70 (oil-soluble azo-based polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) was poured into the flask, and immediately, A dye solution having the composition was added dropwise over 2 hours. Then, after stirring at the same temperature for 3 hours, the mixture was cooled to room temperature to obtain an emulsion C in which resin fine particles (colored resin) containing a coloring agent were dispersed. (Composition of dye solution)

n—butoxymethylacrylamide 17 parts by weight

Glycidyl methacrylate 23 parts by weight

Isobonyl acrylate 4 parts by weight

1 part by weight of Diviel adipate

Orazol Red G (Metal complex of red azo dye, manufactured by Ciba-Geigy) 12.5 parts by weight

50 parts by weight of ion-exchanged water

0.5 parts by weight of sodium dodecyl sulfate

V-65 (Wako Pure Chemical Industries, Ltd., oil-soluble azo polymerization initiator) 1 part by weight 2.5 parts by weight of 1,3-propanediamine is doubled to 100 parts by weight of the obtained emulsion C The mixture was diluted with an amount of ion-exchanged water and added with stirring at room temperature to obtain a colored resin emulsion.

The obtained colored resin emulsion was filtered through a filter having a pore size of 1 m, and the particle size of the colored resin was measured using a laser light scattering particle size distribution analyzer (device name: Microtrack, manufactured by Nikkiso Co., Ltd.). Upon measurement, the average particle size was 92 nm. Example 15

The following aqueous dispersion was charged into a flask, and the liquid temperature was raised to 50 while stirring under a nitrogen stream. Next, 2.5 parts by weight of an ethanol solution containing 0.25 parts by weight of V-70 (oil-soluble azo-based polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) was injected into the flask, and immediately, The dye solution of the composition was added dropwise over 2 hours. Then, after stirring at the same temperature for 3 hours, the mixture was cooled to room temperature to obtain a colored fine particle emulsion D.

(Water dispersion)

Sodium dodecyl sulfate: 1 part by weight

Ion exchange water: 97 parts by weight n-butoxymethyl acrylamide: 5 parts by weight

(Dye solution)

n-butoxymethyl acrylamide: 29 parts by weight

Glycidyl methacrylate:

Dibutyl adipate::

Orazo Red G (Ciba Specialty Chemicals, metal complex of red azo dye): 12.5 parts by weight

Ion exchange water: 50 parts by weight

Sodium dodecyl sulfate: 0.5 parts by weight

V-65 (Wako Pure Chemical Industries, Ltd., oil-soluble azo-based polymerization initiator): 1 part by weight Based on 100 parts by weight of the obtained colored fine particle emulsion D, 0.1 part by weight of y-aminopropyltrimethoxysilane Further, 0.2 parts by weight of 1,2-propanediamine was diluted with 10 times the amount of ion-exchanged water and added with stirring at room temperature to obtain a colored fine particle emulsion.

The obtained colored fine particle emulsion was filtered through a filter having a pore size of 1 m, and the particle size of the colored fine particles was measured using a laser light scattering particle size distribution analyzer (device name: Microtrack, manufactured by Nikkiso Co., Ltd.). However, the average particle size was 90 nm. Comparative Example 6

The colored fine particle emulsion obtained in Comparative Example 4 was subjected to the following printability and resolubility evaluation.

Comparative Example 7

To 100 parts by weight of the colored fine particle emulsion obtained in Comparative Example 4, 0.2 part by weight of N-β (aminoethyl) γ-aminopropyltrimethoxysilane was diluted with 10 times the amount of ion-exchanged water, and the mixture was stirred at room temperature. It was added with stirring to obtain colored fine particle emulsion. (Printability evaluation)

The pigment fine particle emulsions obtained in Examples 13 to 15 and Comparative Examples 6 and 7 were used as inks for ink jet printing with the following composition, and were used as piezo ink jet printers (trade name: PM-7500C, (Seiko Epson Co., Ltd.) to perform a printing test on A4 size paper. Table 4 shows the results.

(Composition of evaluation ink)

Colored fine particle emulsion: 25 parts by weight

Glycerin: 25 parts by weight

Ion-exchanged water: The solid content of the colored fine particle emulsion is 10% by weight. Add the required amount so that it becomes / ₀ . Table 4

The evaluation of printing stability and ink straightness in Table 4 was performed based on the following criteria. Printing stability 〇: A410 sheets can be printed stably.

C: Nozzle clogging occurs when 2 or more A4 sheets and 10 sheets or less, and X: Nozzle clogging occurs when 2 or less A4 sheets are used.

Ink straightness ：: Ink is ejected from the nozzle in a downward direction

X: Ink is ejected obliquely from the nozzle. Example 16 To 100 g of the colored fine particle emulsion obtained in Example 1, 1 g of ammonium persulfate was added to prepare a colored fine particle emulsion for an electrodeposition color filter, and a glass plate coated with ITO and a platinum electrode were placed on this electrode. It was immersed in a colored fine particle emulsion for a color filter, and a voltage was applied at 20 V for 10 seconds to obtain a red color filter on the electrode. The film thickness of this filter was 1.2 / zm.

Example 17

2 parts by weight of sodium dodecyl sulfate (trade name “New Frontier S510”, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 4 parts by weight, 194 parts by weight of deionized water and 10 parts by weight of n-butoxymethyl acrylamide The solution was charged into a separable flask, and the temperature of the solution 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 an oil-soluble azo-based polymerization initiator (trade name “V-70”, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and immediately the colorant was added. 89 parts by weight of n-butoxymethylacrylamide, 1 part by weight of ethylene diol dimethacrylate and a metal complex of red azo dye

(Trade name “Orazol Red G”, manufactured by Ciba Specialty Chemicals) 20 parts by weight of a dye solution was added dropwise over 2 hours. Thereafter, a polymerization reaction was carried out at the same temperature for 3 hours, and then cooled to room temperature to produce a colored fine particle emulsion. The obtained colored fine particle emulsion is filtered through a filter having a pore diameter of 1 / m, and then the particle diameter of the colored fine particles is measured using a laser light scattering particle size distribution analyzer ("Microtrack" manufactured by Nikkiso Co., Ltd.). Was measured, the average particle size was 94 nm. Next, the glass coated with ITO and a platinum electrode were immersed in the colored resin emulsion obtained above, and a voltage of 10 V was applied for 10 seconds to produce a red color filter on the electrode. The thickness of the obtained color filter layer was 1.4 // m. Comparative Example 8

50 parts by weight of n-butoxymethyl acrylamide, 25 parts by weight of ethylene glycol methacrylate and 25 parts by weight of methacrylic acid were dissolved in 300 parts by weight of ethanol, charged in a separable flask, and purged with nitrogen. , Oil-soluble azo polymerization initiator (Product name "V_65", manufactured by Wako Pure Chemical Industries, Ltd.) The polymerization reaction was carried out while dropping 100 parts by weight of an ethanol solution containing 10 parts by weight over 1 hour. Thereafter, the polymerization reaction was continued at the same temperature for 3 hours. Next, add 20 parts by weight of a water-soluble dye as a coloring agent, dissolve and cool to room temperature, and further add 1 part by weight of ammonia water as a pH adjuster 600 parts by weight of water (aqueous solvent) Was added to prepare a colored resin aqueous solution.

Next, 1 part by weight of ammonium persulfate was added to 100 parts by weight of the aqueous solution of the colored resin obtained above, and the mixture was uniformly stirred and mixed to prepare an aqueous solution of a colored resin for electrodeposition. A color filter was produced in the same manner as in Example 17 except that this aqueous solution of a colored resin for electrodeposition was used. The thickness of one layer of the obtained color filter was 1.9 μm.

(Adhesion evaluation)

The ink jet printing inks of Examples 13 to 17 and Comparative Examples 6 to 8 were cast on a glass plate at a thickness of 2 // m and dried at 100 ° C for 1 hour. A cross cut of mm square was applied. The test piece was further subjected to a heating test at 250 ° C. for 1 hour, and then a peeling test was performed using an adhesive tape, and the peeling state of the cross cut portion was visually checked. The results are shown in Table 5. Table 5

The haze of the color filters obtained in Example 17 and Comparative Example 8 and the resolubility of the electrodeposited film were evaluated, and the results are shown in Table 6. The haze was evaluated with a ^ Z meter (model number: TC-H3DPK :, manufactured by Tokyo Denshoku Co., Ltd.). The redissolvability was evaluated by visual observation after immersing the electrodeposited film in water for 2 hours. Table 6

Industrial applicability

Since the present invention has the above-described structure, it has high color density, excellent stability against impacts and the like, and fine particles and fine particles emulsion. It is possible to provide a color filter for a liquid crystal display having excellent adhesion and excellent transparency, and a colored fine particle emulsion for an electrodeposited color filter which can simplify the process because the electrodeposited film does not redissolve. .

Claims

The scope of the claims

1. A colored fine particle obtained by polymerizing a colored composition comprising a monomer composition and a coloring agent is a colored fine particle emulsion dispersed in an aqueous medium,

The monomer composition has the following general formula (I):

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 3 to 6 carbon atoms). And the colored fine particles have a crosslinked structure formed at least on the surface thereof.

A colored fine particle emulsion characterized by the above-mentioned.

2. The colored fine particle emanoreion according to claim 1, wherein the coloring agent is an oil-soluble dye.

3. The coloring agent comprises an anionic dye and the following general formula (II);

· Χ (Π)

(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 1-8 carbon atoms, an aralkyl group having 1-8 carbon atoms or Represents a cycloalkyl group having 7 to 12 carbon atoms, X 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.) The coloring according to claim 1, wherein the salt is a salt obtained by reacting a cationic monomer. Fine particle emulsion.

4. The colored fine particle emulsion according to claim 1, wherein the cross-linked structure has a molecular weight between cross-links of 500 or less.

5. The colored fine particle emulsion according to claim 1, 2, 3 or 4, wherein the monomer composition contains a monomer having two or more vinyl groups.

6. The colored fine particles are obtained by further reacting a crosslinking agent with fine particles obtained by polymerizing a monomer composition containing a monomer having a functional group capable of reacting with a crosslinking agent and a coloring composition comprising a coloring agent. 5. The colored fine particle emulsion according to claim 1, 2, 3, or 4, wherein

7. The colored fine particles are obtained by absorbing a monomer having two or more vinyl groups and an oil-soluble polymerization initiator into fine particles obtained by polymerizing a colored composition comprising a monomer composition and a coloring agent. The colored fine particle emulsion according to any one of claims 1, 2, 3, 4, 5, and 6, wherein the monomer having two or more vinyl groups is polymerized.

8. The colored fine particles are formed by polymerizing a colored composition comprising a monomer composition and a colorant, into a monomer having a glass transition point of a homopolymer of 50 ° C or more and an oil-soluble polymer. After absorbing the initiator, the homopolymer is obtained by polymerizing a monomer having a glass transition point of 50 ° C. or more, wherein the first, second, third, fourth, and fourth claims are characterized in that: The colored fine particle emulsion described in 5 or 6.

9. The monomer composition according to claim 1, wherein the monomer composition contains 1 to 60% by weight of a vinyl monomer containing an epoxy group. Or a colored fine particle emulsion according to item 8.

10. The monomer composition contains 1 to 20% by weight of bulpyridine. 10. The colored fine particle emulsion according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9.

11. The colored fine particle emulsion according to claim 9 or 10, comprising an amine-based silane coupling agent.

1 2. Ink jet printing comprising the colored fine particle emulsion described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 and a humectant. For ink.

1 3. A color filter for a liquid crystal display, characterized by using the ink for ink jet printing according to claim 12.

14. An electrodeposited color filter comprising the colored fine particle emulsion according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, and an electrolyte. Colored fine particle emulsion.

1 5. Colored fine particles obtained from the colored fine particle emulsion according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11.