JP2002121417A - Colored particulate emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored particulate emulsion having a high color density, and excellent shock stability because of hardly causing fusion of fine particles by surface cross-linking, and further to provide an inkjet printing ink comprising the colored particulate emulsion, a color filter for a liquid crystal display, a colored particulate emulsion for an electrodeposited color filter, and a colored fine particle. SOLUTION: This colored particulate emulsion is obtained by dispersing colored fine particles obtained by polymerizing a colored composition comprising a monomer composition and a coloring agent, in an aqueous medium. The monomer composition contains >=10 wt.% monomer represented by general formula (I) (wherein, R1 is a hydrogen atom or a methyl group; and R2 is a 3-6C alkyl group), and the colored fine particles have cross-linked structures formed at least on the surfaces.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored fine particle emulsion having high color density, high stability of fine particles, and excellent stability against impacts, etc., and an ink for ink-jet printing comprising the colored fine particle emulsion. The present invention relates to a color filter for a liquid crystal display, a colored fine particle emulsion for an electrodeposition color filter, and a colored fine particle.

[0002]

2. Description of the Related Art Colored fine particle emulsions in which colored fine particles are dispersed are used for various paints, inks for writing implements, printing inks, inks for ink jet printing, and the like. In ordinary inks and colored emulsions, 1
It is difficult to realize a spectral spectrum of one primary color with different kinds of dyes, and usually, toning is performed by mixing several kinds of dyes. In this case, as the type of the dye, for example, a blue composition in which a phthalocyanine-based cyan dye and an anthraquinone-based cobalt dye are mixed, an azo metal complex-based yellow dye and a phthalocyanine-based cyan dye are mixed. Green compositions and the like can be mentioned. As can be seen from these examples, these materials are mixtures of dyes having completely different chemical structures. Therefore, in order to prepare 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, or the coating film becomes cloudy,
Problems such as insufficient color density of the coating film occur.

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 a nozzle, so that coalescence of fine particles is likely to occur. For this reason, high impact stability is required when using colored emulsions in ink jet printing inks.

One of the conventionally known methods for producing colored fine particles, for example, is to polymerize vinyl chloride alone or by emulsion-polymerizing a monomer copolymerizable with vinyl chloride and vinyl chloride. There is known a method of producing fine particles and dyeing the fine particles 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, JP-A-55-139471 discloses an ink composition for ink jet printing 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 layer 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. According to this method, when the oil-soluble dye composition is added to the aqueous dispersion of the vinyl polymer particles, the vinyl polymer particles are easily aggregated, and the dye is not sufficiently impregnated into the vinyl polymer particles and the color density is reduced. There are issues.

Japanese Patent Application Laid-Open No. 62-95366 discloses that an oil-soluble dye and a polymer composition are dissolved in a hydrophobic organic solvent, and a surfactant and water are added thereto, followed by mixing and emulsification for coloring. A method for producing microparticles is disclosed. In this method, there is a problem that the particle size is not sufficiently reduced, and there is a problem that the surfactant is eliminated due to environmental changes such as concentration, pH, and mechanical impact, and the colored fine particles are easily aggregated.

Japanese Patent Application Laid-Open No. Sho 62-172076 discloses an insoluble polymer dispersed in a liquid medium, the polymer containing an oil-soluble dye, and a nonionic stabilizer permanently bonded to the polymer. A heterophasic ink composition having the structure is disclosed. However, if the nonionic stabilizer is only permanently bound, the stability is not sufficient, and the particle size generally tends to increase.

Japanese Patent Publication No. 52-29336 discloses one or more unsaturated monomers containing butoxymethylacrylamide and one or two unsaturated monomers containing vinyl chloride, styrene and the like. When performing copolymerization with a seed or more, after dissolving or dispersing a dye in the unsaturated monomer, copolymerization of the unsaturated monomer is performed to produce colored fine particles in which the inside is colored with a dye. A method for doing so is disclosed. However, these colored fine particles do not take into account physical properties such as particle size and mechanical stability required for ink-jet printing inks.

As a method for forming a color filter of a liquid crystal display element, there is an electrodeposition method in addition to the above-mentioned printing by ink jet. The electrodeposition method is an excellent method in that the precision of pattern formation is excellent and the process is relatively simple. JP-A-8-2
As disclosed in Japanese Patent Application Laid-Open No. 92314, conventionally, in the electrodeposition method, a water-soluble resin such as an acrylic resin or a polyester resin containing an acid group is blended with a crosslinking agent such as melamine, epoxy and isocyanate and a pigment. A method using a liquid is known. However, since the electrodeposited film has resolubility, it was necessary to electrodeposit the next color after performing a cross-linking treatment with light or heat for each color when trying to obtain pixels of a plurality of colors. . Further, an electrodeposition color filter using a pigment has poor smoothness on the surface of the film, and has a problem in transparency. Furthermore, since the ratio between the coloring agent and the binder resin changes depending on the ratio of the ionic group, adjustment is required.

[0011]

DISCLOSURE OF THE INVENTION In view of the above, the present invention is directed to a colored fine particle emulsion having a high color density and an excellent impact stability due to the difficulty of coalescence of fine particles due to surface crosslinking.
An object of the present invention is to provide an ink for inkjet printing, a color filter for a liquid crystal display, a colored fine particle emulsion for an electrodeposition color filter, and colored fine particles comprising the colored fine particle emulsion.

[0012]

The present invention provides 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, The monomer composition has the following general formula (I);

[0013]

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(Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 3 to 6 carbon atoms). And
The colored fine particles are colored fine particle emulsions having at least a crosslinked structure formed on the surface thereof. Hereinafter, the present invention will be described in detail.

The colored fine particle emulsion of the present invention is obtained by dispersing colored fine particles obtained by polymerizing a colored composition comprising a monomer composition and a coloring agent 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 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, a cross-linked structure is usually formed by a reaction including multi-step steps. You. 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.

In the case of producing colored fine particles having a crosslinked structure in the whole fine particles, the above monomer composition is a vinyl monomer composition from the viewpoint of easy control of particle size and production efficiency.
It is preferable to obtain colored fine particles by emulsion polymerization.

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

In the present invention, the monomer composition contains at least 10% by weight of a monomer represented by the above general formula (I) (hereinafter also referred to as a polymerizable monomer (I)). Things. In the polymerizable monomer (I), R ¹ represents a hydrogen atom or a methyl group. Therefore, the polymerizable monomer (I) is an acrylamide derivative or a methacrylamide derivative.

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

The polymerizable monomer (I) has a function of dissolving the dye at a high concentration and causes a cross-linking reaction by heat. Sex can be given.

When the content of the polymerizable monomer (I) is less than 10% by weight, it is difficult to dissolve the dye at a high concentration, and when the colored fine particles are made of a thermosetting resin, the crosslinking is difficult. Is insufficient, and the solvent resistance and the chemical resistance become insufficient, so that the above range is preferable. It is more preferably at least 40% by weight, still more preferably at least 70% by weight.

The coloring agents usually used in the colored fine particle emulsion include, for example, dyes and pigments. As the dye, for example, acid dyes, basic dyes, direct dyes, disperse dyes, oil-soluble dyes and the like can be used, but from the viewpoint of high durability, good dispersion in the resin,
As the colorant used in the present invention, an oil-soluble dye is preferable.

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. of 10% by weight or less. Is more preferable.

The solubility in an organic solvent at 20 ° C. is 1% by weight or more, the solubility in water at 20 ° C. is 1% by weight or less, and the solubility in water at 100 ° C. is 10% by weight.
The following oil-soluble dyes include, for example, azo dyes,
Examples include anthraquinone dyes, phthalocyanine dyes, triphenylmethane dyes, and azo metal complex dyes. In terms of the color index number, solv
ent blue 44, 45, 59, 104; solv
ent red 24, 68, 89, 124; solvent
nt yellow 13, 14, 33, 79, 93; v
at blue 1 and 6; va yellow 6 and the like. These may be used alone or in combination of two or more.

The amount of the oil-soluble dye is preferably 1 to 50 parts by weight based on 100 parts by weight of the monomer composition. If the amount exceeds 50 parts by weight, the concentration of the colorant becomes too high to make it difficult to add, and the colorant may be separated during polymerization. More preferably 5 to 30
Parts by weight.

As the coloring agent used in the present invention, a salt obtained by reacting an anionic dye with a cationic monomer represented by the following general formula (II) is also preferably mentioned.

[0029]

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Where R³Represents a hydrogen atom or a methyl group
Then R⁴, R⁵, R⁶Are each independently a group having 1 carbon atom
Alkyl group, aralkyl group having 1 to 8 carbon atoms or carbon
X represents a cycloalkyl group having a prime number of 7 to 12, and X represents
Represents an atom⁴, R⁵, R ⁶Included in the group represented by
The total number of carbon atoms is 8 or more.

The cationic represented by the general formula (II)
The monomer is relatively strong in hydrophobicity, and is combined with the anionic dye.
The salt can be precipitated by the reaction of R above⁴,
R⁵, R⁶Are each independently an alkyl having 1 to 8 carbon atoms
Kill group, aralkyl group having 1 to 8 carbon atoms or 7 to 1 carbon atom
2 represents a cycloalkyl group. R above ⁴, R⁵, R⁶so
Examples of the group represented include a methyl group, an ethyl group, n
-Propyl group, i-propyl group, benzyl group, cyclohexane
Xyl groups 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,
Examples include an ethyl group, an ethyl group and a benzyl group.

When the total number of carbon atoms contained in the groups represented by R ⁴ , R ⁵ , and R ⁶ is less than 8, the cationic monomer has high hydrophilicity and reacts with the anionic dye by the reaction. It is not preferable because it is difficult to form a hydrophobic salt. The anionic dye is not particularly limited, and examples thereof include an azo dye, an anthraquinone dye, and a triphenylmethane 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 a polymer of colored fine particles. Since the anionic dye is incorporated therein, the anionic dye is firmly fixed in the colored fine particles by ionic bonding.

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 following monomer composition is used.
It is preferable to use those containing 90% by weight or more of the polymerizable monomer (I).

In the case where the colored fine particles have a crosslinked structure in the whole fine particles, the monomer composition may contain 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 ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, allyl methacrylate, vinyl methacrylate, and glycerol dimethacrylate. , Divinylbenzene, triallyl 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. If the amount is less than 0.1% by weight, the hardness of the coating film obtained by the obtained colored fine particle emulsion may decrease, or the solvent resistance may decrease. If the amount exceeds 30% by weight, the solubility of the coloring agent may be reduced. In addition to the reduction, aggregation of emulsion fine particles, precipitation of dye, and the like are likely to occur. More preferably 0.1 to 10% by weight,
The content is more preferably 0.5 to 10% by weight, and particularly preferably 0.5 to 5% by weight.

The colored fine particles preferably have a uniform cross-linked structure on the surface and inside thereof, and the degree of cross-linking is preferably a molecular weight between cross-links of 5,000 or less. The molecular weight between crosslinks indicates an average value of 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 a numerical value theoretically calculated from the charged amount. The smaller the value, the higher the degree of crosslinking. Σ (Wi × ri) / Σ (ni × ri) (1)

In the formula, Wi is the molecular weight of monomer i, which is a constituent of the polymer, and ri is the molar ratio of monomer i (Σri =
1) and ni represent the number of double bonds that can be incorporated into the main chain skeleton contained in one molecule of the monomer i (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 colored composition is dispersed in water in the presence of an emulsifier and emulsion polymerization is performed using a water-soluble polymerization initiator; A method in which an oil-soluble polymerization initiator is dissolved in a product, dispersed in water in the presence of an emulsifier, and then emulsion-polymerized.

The polymerization initiator is not particularly limited.
For example, oil-soluble or water-soluble organic azo compounds, potassium persulfate, inorganic peroxides such as ammonium persulfate, organic peroxides, and redox compositions combining inorganic peroxides and reducing agents such as sulfites. No. The water-soluble organic azo compound includes a cationic compound and an anionic compound.

Among these polymerization initiators, organic azo compounds are preferable, and the 10-hour half-life temperature is 40 to 80 ° C.
Are more preferred. There is no particular limitation on which organic azo compound is used. For example, an azo metal complex dye and / or a salt obtained by reacting an anionic dye with a cationic monomer as an oil-soluble dye. When is used, it is preferable to use an oil-soluble organic azo compound. As a result, a colored fine particle emulsion having excellent optical properties and durability 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. When the amount is less than 0.1 part by weight, the polymerization reaction may not proceed smoothly. On the other hand, when the amount exceeds 10 parts by weight, the molecular weight of the obtained vinyl resin may be too low. More preferably, it is 0.2 to 5 parts by weight.

The emulsifier is not particularly restricted but includes, for example, anionic, cationic and nonionic surfactants. Among them, anionic surfactants are preferred. Cationic surfactants do not have strong dispersibility,
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 alkyl sulfate, and alkyl sulfonates such as sodium alkyl sulfonate and ammonium alkyl sulfonate. Of these, alkyl sulfonates are preferred because they have the advantage of not adversely affecting the physical properties of the coating film.

Further, as the anionic surfactant,
Anionic surfactants having a polymerizable group can also be used. Examples of the anionic surfactant having a polymerizable group include sulfonic acid (salt) type and carboxylic acid (salt)
Type, phosphate ester (type) and the like. Among these, a phosphate ester having a polymerizable unsaturated bond is
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. The amount of the emulsifier is not particularly limited, but the weight ratio of the colored composition to the aqueous solution of the emulsifier (colored composition / aqueous solution of the emulsifier) is preferably 1/5 to 1/1. The reaction temperature of the emulsion polymerization is not particularly limited, but is usually preferably 10 to 100 ° 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 type 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, and the temperature is increased to a reaction temperature while stirring under a nitrogen stream, and then a polymerization initiator is injected into the flask, and an oil-soluble dye is added. Is added dropwise over 1 to 2 hours, and at the same temperature, 3 to 4
After stirring for a period of time, emulsion polymerization is performed using a method such as cooling to room temperature, whereby the colored fine particle emulsion of the present invention can be produced.

Further, the coloring composition is dispersed in water in the presence of an emulsifier, and a polymerization initiator is further added to obtain a dispersion of seed particles in advance. The colored fine particle emulsion of the present invention can also be obtained by a seed polymerization technique in which a dispersion obtained by dispersing a mixture with a polymerization initiator in water in the presence of an emulsifier is gradually dropped.

In the colored fine particle emulsion of the present invention, when a crosslinked structure is introduced only on the surface of the colored fine particles, or when the crosslinked density is formed unevenly between the surface and the inside of the colored fine particles, Is made denser than the inside by crosslinking the surface of fine particles prepared in advance. 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.

The method for producing the surface crosslinked colored fine particles is, for example, 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. A method in which a fine particle is further reacted with a crosslinking agent may be used.

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

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. Such compounds include, for example, ethylenediamine, 1,2-propanediamine, 1,3-
Polyfunctional amine compounds having an amino group such as propanediamine and diethylenetriamine; polyol compounds having a hydroxyl group such as ethylene glycol and glycerin; polycarboxylic acid compounds having a carboxylic acid such as succinic acid, adipic acid and maleic acid; maleic anhydride And acid anhydrides such as phthalic anhydride; and polyfunctional isocyanate compounds and polyfunctional epoxy compounds.

The amount of the cross-linking agent to be added is determined by the relationship between the amount of the functional group in the cross-linking agent and the amount of the functional group capable of reacting with the cross-linking agent in the fine particles, and the former is equal to or less than the latter. It is preferably a quantitative ratio. If the former exceeds the equivalent of the latter,
Since a plurality of functional groups of the cross-linking agent cannot react with each other to seal the cross-linking point, a sufficient cross-linking effect cannot be obtained, which is not preferable. In particular, in order for the crosslinking agent to sufficiently allow the functional group on the surface of the fine particles to easily react with the crosslinking, it is preferable that the ratio be such a ratio.

As described above, in the method of cross-linking the surface of the previously prepared fine particles with a cross-linking agent and introducing a desired cross-linked structure, the degree of cross-linking is represented by the molecular weight between cross-links defined by the following formula (2). The molecular weight between crosslinks is 5
000 or less. More preferably 40
00 or less. Σ (Wi × ri) / (Σni × ri + Σmi × ri) (2)

In the formula, Wi is the molecular weight of the constituent monomer i, ri is the molar ratio of the monomer i (Σri = 1), and ni is the main chain skeleton contained in one molecule of the monomer i. (However, ni = 0 in the case of a monofunctional monomer)
And mi represents the number of functional groups that become 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 approximately zero and is ignored.

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

As another method for producing the above surface-crosslinked colored fine particles, for example, a fine particle obtained by polymerizing a colored composition comprising a monomer composition and a colorant is added to a monomer having two or more vinyl groups. And a method of absorbing the oil-soluble polymerization initiator and then polymerizing the monomer having two or more vinyl groups. As the monomer having two or more vinyl groups, the same one as described above is used.

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

Examples of the oil-soluble polymerization initiator include, for example,
Organic peroxides such as benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, di-t-butyl peroxide; azobisisobutyronitrile; Organic azo compounds such as azobiscyclohexacarbonitrile and azobis (2,3-dimethylvaleronitrile) are exemplified.

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 used. This is carried out by finely dispersing the agent in water and stirring with the fine particles for 1 to 24 hours. The polymerization temperature of the absorbed monomer having two or more vinyl groups is selected according to the polymerization initiator.
It is in the range of 0 ° C, more preferably in the range of 40 to 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 in at least the surface layer are preferable. . When the glass transition point of the homopolymer is less than 50 ° C., the colored fine particles are likely to coalesce during inkjet printing.

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

In order for the colored fine particle emulsion of the present invention to exhibit resolubility, it is preferable that the monomer composition contains 1 to 60% by weight of a vinyl monomer having an epoxy group.

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 left to dry at room temperature and immersed in water becomes a coating film piece having a size (longest diameter) of 100 μm or less (longest diameter). If the size (longest diameter) of the coating film piece exceeds 100 μm and exceeds 5%, resolubility is lost and clogging of the nozzle hole is caused.

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

The 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 at a temperature of 5 to 38 ° C and a humidity of 30 to 95% for 5 minutes to 1000 hours. If the time is less than 5 minutes, a coating film is not formed, so it cannot be said that the film is re-dissolved. If the time exceeds 1000 hours, factors other than drying, such as crosslinking and decomposition of the resin, are added. More preferably, drying is performed for 10 minutes to 100 hours in an environment of a temperature of 5 to 38 ° C and a humidity of 30 to 95%.

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 from the viewpoint of compatibility with the polymerizable monomer (I), solubility of the oil-soluble dye, and adhesion to the substrate.

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 base material is hardly recognized, and 60% by weight is reduced. If it exceeds, it may be difficult to polymerize colored fine particles containing a coloring agent having a preferable particle size.

As the vinyl-based monomer for exhibiting redispersibility in the dried colored fine particle emulsion, those having an ionic structure in an aqueous solvent can be suitably used. Such vinyl monomers include, for example, vinylpyridine acrylic acid, methacrylic acid, maleic acid, maleic anhydride, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, acrylamide-t-butylsulfonic acid, Ethyl dimethylaminoacrylate, itaconic acid, undecylenic acid, crotonic acid, citraconic acid,
N- [3- (dimethylamino) propyl] acrylamide and the like. Of these, vinyl pyridine is most suitable in terms of affinity with the dye.

When such a colored fine particle emulsion having re-solubility in water is used as an ink for ink-jet printing, it has re-solubility in water as a solvent as described above. Agglomerates are not easily formed, and even if agglomerates are generated, they are quickly washed away due to resolubility, so that the nozzles are not clogged and the dischargeability is good.

An epoxy group is introduced into the colored fine particles,
Further, by containing the amine 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, the total number of carbon atoms in one molecule is 3
0 or less, and the number of carbon atoms acting as a silane coupling agent is 1
An alkoxysilane of 0 or less is used. 3 total carbon atoms
If it exceeds 0, dispersibility in the colored fine particle emulsion may be deteriorated, and if the number of carbon atoms of the alkoxide on the silicon atom exceeds 10, the substitution reaction on the silicon atom may be difficult to proceed.

Examples of the amine silane coupling agent include N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane and N-β (aminoethyl) γ
-Aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-
Phenyl-γ-aminopropyltrimethoxysilane, γ
-Aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane and the like. These may be used alone or in combination of two or more.

The content of the amine 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. When the amount is less than 0.01 part by weight, there is no effect of addition, and when the amount exceeds 10 parts by weight, the amount is too large and does not mix with the colored fine particle emulsion, or the colored fine particles aggregate with impairing the stability of the colored fine particle emulsion. Sometimes.

The method of 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 of adding the amine-based silane coupling agent to an aqueous medium before polymerization of the colored fine particles; A method of adding to the obtained colored fine particle emulsion is exemplified.

An ink for ink jet printing can be prepared by adding a humectant to the colored fine particle emulsion of the present invention. The humectant has a boiling point of 10
At 0 ° C. or higher, it is preferably a water-soluble organic compound, for example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, dimethyl sulfoxide, Pyrrolidone and its derivatives, alcohols and the like can be mentioned.

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 ink jet 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.

A color filter for a liquid crystal display by printing the above-mentioned ink for inkjet printing having three primary colors of red, green and blue or complementary colors of cyan, magenta and yellow on a glass substrate or a resin substrate of a liquid crystal display panel by an ink jet method. Can be produced. A color filter for a liquid crystal display using the ink for inkjet printing is also one of the present invention.

A colored fine particle emulsion for an electrodeposition color filter can be obtained by adding an electrolyte to the colored fine particle emulsion of the present invention. The electrolyte is not particularly limited as long as it is a water-soluble salt, and examples thereof include inorganic salts such as sodium chloride, potassium chloride, ammonium chloride, and ammonium perchlorate;
Alkyl sulfates such as ammonium alkyl sulfate; anionic surfactants such as alkyl sulfonates such as sodium alkyl sulfonate and ammonium alkyl sulfonate; aliphatic amine salts, benzalkonium salts, pyridinium salts, imidazolinium salts, etc. And cationic surfactants.

The concentration of the above electrolyte is 0.5 to 5% by weight in the colored fine particle emulsion for an electrodeposition color filter.
It is preferable that If the amount is less than 0.5% by weight, the resulting colored resin emulsion may have low electrodeposition properties, and a high voltage may be required for electrodeposition. The moisture resistance and water resistance of the coating film may decrease. The solid content concentration of the colored fine particles in the colored fine particle emulsion for an electrodeposition color filter is preferably 5 to 50% by weight.

A liquid crystal display panel on which a transparent electrode such as ITO is formed by an electrodeposition method using ink composed of an electrodeposition color filter colored fine particle emulsion having three primary colors of red, green and blue or complementary colors of cyan, magenta and yellow. An electrodeposited color filter can be manufactured by forming a color filter layer on a glass substrate or a resin substrate for use. As a method of producing the electrodeposited color filter, the electrodeposited color filter is formed by immersing a substrate for a liquid crystal display panel on which a transparent electrode is formed and a counter electrode in a colored fine particle emulsion for an electrodeposited color filter, and applying an electric field. .

The potential to be applied is preferably 5 to 50 V, and the application time is preferably 3 to 60 seconds. The thickness of the formed color filter layer is
It is preferably from 0.3 to 3 μm.

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

After the formation of the above-mentioned electrodeposited color filter, a heat treatment is carried out, whereby a crosslinking reaction by the polymerizable monomer (I) proceeds, and the solvent resistance can be increased. The heat treatment conditions are a temperature of 120 to 250 ° C. and a time of 10 to 60.
Minutes is preferred. 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 colored fine particle emulsion are also one of the present invention.

[0089]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 2 parts by weight of sodium dodecyl sulfate, 198 parts by weight of deionized water and 5 parts by weight of n-butoxymethylacrylamide were charged into a flask, and the mixture was heated to 50 ° C. while stirring under a nitrogen stream. Was. Next, 5 parts by weight of an ethanol solution containing 0.5 parts by weight of V-70 (manufactured by Wako Pure Chemical Industries, Ltd., oil-soluble azo-based polymerization initiator) was poured into the flask, and immediately, a coloring having the following composition was performed. The aqueous dispersion 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.

The obtained colored fine particle emulsion was prepared with a pore size of 1
After filtering through a μm filter and measuring the particle size of the colored fine particles using a laser light scattering particle size distribution analyzer (device name: Microtrack, manufactured by Nikkiso Co., Ltd.), the average particle size was 1
45 nm. The molecular weight between crosslinks calculated from the composition was 2876.

(Coloring composition) n-butoxymethylacrylamide (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 mol part: ratio 0.620) Fancryl FA-731A (Tris manufactured by Hitachi Chemical Co., Ltd.) (2-hydroxyethyl) isocyanuric acid acrylate, trifunctional monomer: molecular weight 423): 5 parts by weight (0.012 mol part: ratio 0.015) Orazole Red G (manufactured by Ciba Specialty Chemicals, red azo) Metal complex of 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 EA170 (Nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 6 parts by weight A dispersion medium is added to the above colored composition with stirring, and the colored composition is obtained. Was obtained.

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 following composition. The average particle size of the fine particles of the emulsion thus obtained was 210 nm. The molecular weight between fine particle surfaces crosslinked calculated from the composition was 959.

(Coloring composition) n-butoxymethylacrylamide (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 part: ratio 0.601) Fancryl FA-731A (Tris manufactured by Hitachi Chemical Co., Ltd.) (2-hydroxyethyl) isocyanuric acid acrylate, trifunctional monomer: molecular weight 423): 15 parts by weight (0.035 mol part: ratio 0.047) Orazole Red G (manufactured by Ciba Specialty Chemicals, red azo) Metal complex of dye): 30 parts by weight V-65 (molecular weight: 248): 2 parts by weight (0.008 mol part: ratio 0.011)

(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 is added to the above colored composition with stirring, and the colored composition is obtained. Was obtained.

Example 3 An 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 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 carry out a crosslinking treatment on the surface of the fine particles. It is considered that all glycidyl groups on the surface of the fine particles became cross-linking points by this operation, and a cross-linked structure was formed. The molecular weight between fine particle surfaces crosslinked calculated from the composition was 1787.

(Coloring composition) n-butoxymethylacrylamide (molecular weight: 157):
45 parts by weight (0.287 mol part: ratio 0.355) Methyl methacrylate (molecular weight 100): 45 parts by weight (0.450 mol part: ratio 0.558) Glycidyl methacrylate (molecular weight 142): 5 parts by weight ( 0.035 mol part: ratio 0.044) 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 EA170 (Nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 6 parts by weight A dispersion medium is added to the above colored composition with stirring, and the colored composition is obtained. Was obtained.

Example 4 An 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 fine particles of the emulsion thus obtained was 112 nm.

Next, 13.0 parts by weight of a 5% by weight aqueous solution of 1,2-propanediamine was slowly and gradually added to the obtained emulsion while stirring at room temperature to carry out a crosslinking treatment on the surface of the fine particles. It is considered that all glycidyl groups on the surface of the fine particles became cross-linking points by this operation, and a cross-linked structure was formed. The molecular weight between fine particle surface crosslinks calculated from the composition was 1190.

(Coloring composition) n-butoxymethylacrylamide (molecular weight: 157):
45 parts by weight (0.287 mol part: ratio 0.356) Methyl methacrylate (molecular weight 100): 45 parts by weight (0.450 mol part: ratio 0.559) Glycidyl methacrylate (molecular weight 142): 5 parts by weight ( 0.035 mol part: ratio 0.044) divinyl adipate (bifunctional monomer: molecular weight 19)
8): 5 parts by weight (0.025 mol part: ratio 0.031) Orazole Red G (a metal complex of a red azo dye manufactured by Ciba Specialty Chemicals): 30 parts by weight V-65 (molecular weight 248): 2 Parts by weight (0.008 mol parts: 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 is added to the above colored composition with stirring, and the colored composition is obtained. Was obtained.

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 following composition. 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 and gradually added to carry out a crosslinking treatment on the surface of the fine particles. It is considered that all glycidyl groups on the surface of the fine particles became cross-linking points by this operation, and a cross-linked structure was formed. The molecular weight between fine particles surface cross-links calculated from the composition was 1092.

(Coloring composition) n-butoxymethylacrylamide (molecular weight: 157):
40 parts by weight (0.255 mol part: ratio 0.321) Methyl methacrylate (molecular weight 100): 45 parts by weight (0.450 mol part: ratio 0.567) Glycidyl methacrylate (molecular weight 142): 10 parts by weight ( 0.070 mol part: ratio 0.089) divinyl adipate (bifunctional monomer: molecular weight 19)
8): 2 parts by weight (0.010 mol part: ratio 0.013) 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 mol parts: 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 is added to the above color composition with stirring, and the color composition is obtained. Was obtained.

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 following composition. 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 and gradually added to the obtained emulsion while stirring at room temperature to carry out a crosslinking treatment on the surface of the fine particles. It is considered that all glycidyl groups on the surface of the fine particles became cross-linking points by this operation, and a cross-linked structure was formed. Further, the molecular weight between fine particle surfaces crosslinked calculated from the composition was 1377.

(Coloring composition) n-butoxymethylacrylamide (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 part: ratio 0.575) Glycidyl methacrylate (molecular weight 142): 10 parts by weight ( 0.070 mol parts: 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 mol) (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 is added to the above colored composition with stirring, and the colored composition is added. Was obtained.

Example 7 2 parts by weight of sodium dodecyl sulfate, 4 parts by weight of New Frontier S510, 194 parts by weight of deionized water, and
A flask was charged with 10 parts by weight of n-butoxymethylacrylamide, and the solution was heated to 50 ° C. while stirring under a nitrogen stream.
Raised to.

Next, 10 parts by weight of an ethanol solution containing 0.5 parts by weight of V-70 (oil-soluble azo polymerization initiator, manufactured by Wako Pure Chemical Industries, Ltd.) was injected into the flask, and immediately the following composition was obtained. 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 fine particle emulsion.

0.1 part by weight of V-65 (oil-soluble azo-based polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 5 parts by weight of trimethylolpropane triacrylate in 30 parts by weight of ion-exchanged water and 1 part by weight of ethanol And 0.3 parts 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 fine particle emulsion, and the mixture was stirred at 25 ° C. and 200 rpm for 3 hours, so that trimethylolpropane triacrylate was absorbed by the fine particles in the emulsion. The temperature of this emulsion was raised to 50 ° C., and the mixture was reacted for 8 hours while stirring under nitrogen to obtain a colored fine particle emulsion having a trimethylolpropane triacrylate polymer on the surface.

The obtained emulsion of colored fine particles was adjusted to a pore size of 1
After filtering through a μm filter and measuring the particle size of the colored fine particles using a laser light scattering particle size distribution analyzer (device name: Microtrack, manufactured by Nikkiso Co., Ltd.), the average particle size was 1
32 nm.

(Coloring composition) n-butoxymethylacrylamide: 89 parts by weight Ethylene glycol dimethacrylate (bifunctional monomer): 1 part by weight Orazole Red G (manufactured by Ciba Specialty Chemicals, metal complex of red azo dye): 20 parts by weight

Example 8 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 in place of trimethylolpropane triacrylate. Was obtained.
The obtained colored fine particle emulsion was filtered with a filter having a pore size of 1 μm, and the particle size of the colored fine particles was measured.
Average particle size was 120 nm

Example 9 2 parts by weight of sodium dodecyl sulfate, 4 parts by weight of New Frontier S510, 194 parts by weight of deionized water, and
A flask was charged with 10 parts by weight of n-butoxymethylacrylamide, and the solution was heated to 50 ° C. while stirring under a nitrogen stream.
Raised to.

Next, 10 parts by weight of an ethanol solution containing 0.5 parts by weight of V-70 (oil-soluble azo polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) was injected into the flask, and immediately, the following composition was obtained. The dye solution was added dropwise over 2 hours, then stirred at the same temperature for 3 hours, cooled to room temperature, and emulsified with resin fine particles containing a colorant (hereinafter referred to as emulsion A).
I got

(Composition of Dye Solution) n-butoxymethylacrylamide: 89 parts by weight Ethylene glycol dimethacrylate: 1 part by weight Orazole Red G (manufactured by Ciba Specialty Chemicals, metal complex of red azo dye): 20 parts by weight

Next, V-65 (oil-soluble azo polymerization initiator, manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 5 parts by weight of methyl methacrylate and 1 part by weight of ethanol in 30 parts by weight of ion-exchanged water. 1 part by weight and sodium dodecyl sulfate 0.
3 parts by weight were added, and the mixture was emulsified with a homogenizer.

The obtained emulsion was added to 100 parts by weight of the emulsion A, and the mixture was stirred at 200 rpm for 3 hours at a temperature of 25 ° C. to absorb the monomer and the polymerization initiator into the fine resin particles in the emulsion A. I let it.

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 polymethyl 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, fine particles were not crosslinked.

(Coloring composition) n-butoxymethylacrylamide (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 mol part: ratio 0.623) Orazole Red G (manufactured by Ciba Specialty Chemicals) Red azo dye metal complex): 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 EA170 (Nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 6 parts by weight A dispersion medium is added to the above colored composition with stirring, and the colored composition is added. Was obtained.

Comparative Example 2 Using the emulsion used in Example 3,
-Evaluation was carried out without adding propanediamine. This emulsion had no crosslinked structure 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 were subjected to a piezo ink jet printer (trade name: PM-750C, Seiko Epson) Print test. The results are shown in Table 1.

(Composition of Ink for Evaluation) Colored fine particle emulsion: 25 parts by weight Glycerin: 25 parts by weight Ion-exchanged water: solid content of colored fine particle emulsion is 10
Add the required amount to give the weight%.

[0131]

[Table 1]

The evaluation of printing stability and ink rectilinearity in Table 1 was performed based on the following criteria. Printing stability ：: A4 10 sheets can be printed stably. C: A4 clogging of nozzles occurs when 2 or more sheets and 10 sheets or less. ×: clogging of the nozzle occurs with two or less A4 sheets. Ink straightness ：: Ink is ejected from the nozzle in a hanging direction. X: Ink is ejected from the nozzle obliquely.

Example 10 1 part by weight of sodium dodecyl sulfate, 97 parts by weight of ion-exchanged water and 5 parts by weight of n-butoxymethylacrylamide were charged into a flask, and the 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 an oil-soluble azo polymerization initiator (trade name “V-70” manufactured by Wako Pure Chemical Industries, Ltd.) was injected into the flask, and immediately, An aqueous dispersion of a dye solution having the composition shown in Table 2 was added dropwise at the same temperature over 3 hours. After stirring at the same temperature for 3 hours, the mixture was cooled to room temperature to obtain a colored resin fine particle emulsion.

[0134]

[Table 2]

Example 11 The composition of the dye solution used in Example 10 is shown in Table 2 above.
An emulsion was prepared in the same manner as in Example 10 except that the composition was changed to the composition shown in Table 1.

Example 12 The composition of the dye solution used in Example 10 is shown in Table 2 above.
An emulsion was prepared in the same manner as in Example 10 except that the composition was changed to the composition shown in Table 1.

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 (manufactured by Wako Pure Chemical Industries, Ltd., oil-soluble azo polymerization initiator) was injected into the flask, and immediately, a dye having the following composition was used. The solution 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: 1 part by weight Deionized water: 97 parts by weight n-butoxymethylacrylamide: 5 parts by weight

(Dye solution) Tetrahydrofurfuryl acrylate: 45 parts by weight Orazole Red G (manufactured by Ciba Specialty Chemicals, metal complex of red azo dye): 12.5 parts by weight Ion exchange water: 50 parts by weight dodecyl sulfate Sodium: 0.5 part by weight V-65 (manufactured by Wako Pure Chemical Industries, oil-soluble azo polymerization initiator): 1 part by weight

The obtained emulsion of colored fine particles was prepared by
After filtering through a μm filter and measuring the particle size of the colored fine particles using a laser light scattering particle size distribution analyzer (device name: Microtrack, manufactured by Nikkiso Co., Ltd.), the average particle size was 1
22 nm.

Comparative Example 4 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 (manufactured by Wako Pure Chemical Industries, Ltd., oil-soluble azo polymerization initiator) was injected into the flask, and immediately, a dye having the following composition was used. The solution 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: 1 part by weight Deionized water: 97 parts by weight n-butoxymethylacrylamide: 5 parts by weight

(Dye solution) Methyl methacrylate: 22 parts by weight Acrylonitrile: 23 parts by weight Orazole Red G (manufactured by Ciba Specialty Chemicals, metal complex of red azo dye): 12.5 parts by weight Ion exchange water: 50 parts by weight Part: sodium dodecyl sulfate: 0.5 part by weight V-65 (manufactured by Wako Pure Chemical Industries, oil-soluble azo polymerization initiator): 1 part by weight

The obtained colored fine particle emulsion was treated with a pore size of 1
After filtration through a μm filter, 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.).
It was 8 nm.

Comparative Example 5 The composition of the dye solution used in Example 10 is shown in Table 2 above.
An emulsion was prepared in the same manner as in Example 10 except that the composition was changed to the composition shown in Table 1.

[Evaluation of Resolubility] The colored fine particle emulsions obtained in Examples 10 to 12 and Comparative Examples 3 to 5
After being applied to a glass plate of mx 100 mm, it was left to dry in an environment at 23 ° C and a humidity of 65% for 30 minutes and dried. 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. When taking out, the glass plate was taken out by slightly shaking it two or three times. The remaining water was filtered through a stainless wire mesh having a mesh size of 90 μm in the example and 106 μm in the comparative example, and the ratio of the weight of the coating film remaining on the wire mesh to the total weight of the coating film was measured. The results are shown in Table 3.

The colored fine particle emulsions obtained in Examples 10 to 12 and Comparative Examples 3 to 5 were used as inks for ink jet printing with the following composition, and were piezo ink jet printers (trade name: PM-750C, manufactured by Seiko Epson Corporation). A), a print test was performed on A4 size paper. The results are also shown in Table 3.

(Composition of evaluation ink) Colored fine particle emulsion: 25 parts by weight Glycerin: 25 parts by weight Ion-exchange water: solid content of colored fine particle emulsion is 10
Add the required amount to give the weight%.

[0149]

[Table 3]

The evaluation of printing stability and ink rectilinearity in Table 3 was performed based on the following criteria. Printing stability ：: A4 10 sheets can be printed stably. C: A4 clogging of nozzles occurs when 2 or more sheets and 10 sheets or less. ×: clogging of the nozzle occurs with two or less A4 sheets. Ink straightness ：: Ink is ejected from the nozzle in a hanging direction. X: Ink is ejected from the nozzle obliquely.

Example 13 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 (manufactured by Wako Pure Chemical Industries, Ltd., oil-soluble azo polymerization initiator) was injected into the flask, and immediately, a dye having the following composition was used. The solution 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 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-butoxymethylacrylamide: 17 parts by weight Glycidyl methacrylate: 23 parts by weight Isobonyl acrylate: 4 parts by weight Divinyl adipate: 1 part by weight Orazole Red G (manufactured by Ciba Specialty Chemicals, red azo Metal complex of dye): 12.5 parts by weight Ion exchange water: 50 parts by weight Sodium dodecyl sulfate: 0.5 parts by weight V-65 (manufactured by Wako Pure Chemical Industries, Ltd., oil-soluble azo polymerization initiator): 1 part by weight

The obtained colored fine particle emulsion B100
0.2 parts by weight of N-β (aminoethyl) γ-aminopropyltrimethoxysilane 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 prepared using a pore size of 1
After filtration through a μm filter, 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.).
It was 2 nm.

Example 14 A flask was charged with 1 part by weight of sodium dodecyl sulfate, 97 parts by weight of ion-exchanged water and 5 parts by weight of n-butoxymethylacrylamide, and the solution was heated to 50 ° C. while stirring under a nitrogen stream. Was. Next, 2.5 parts by weight of an ethanol solution containing 0.25 parts by weight of V-70 (manufactured by Wako Pure Chemical Industries, Ltd., oil-soluble azo-based polymerization initiator) was injected into the flask, and immediately the mixture was composed of the following composition. The dye solution 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 colorant were dispersed.

(Composition of Dye Solution) n-butoxymethylacrylamide: 17 parts by weight Glycidyl methacrylate: 23 parts by weight Isobonyl acrylate: 4 parts by weight Divinyl adipate: 1 part by weight 12.5 parts by weight Ion-exchanged water: 50 parts by weight Sodium dodecyl sulfate: 0.5 parts by weight V-65 (Wako Pure Chemical Industries, oil-soluble azo-based polymerization initiator): 1 part by weight

To 100 parts by weight of the obtained emulsion C, 2.5 parts by weight of 1,3-propanediamine was diluted with twice the amount of ion-exchanged water, and added while stirring at room temperature.
A colored resin emulsion was obtained.

The obtained colored resin emulsion was treated with a pore size of 1
After filtration through a μm filter, 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.). 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 ° 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 (manufactured by Wako Pure Chemical Industries, Ltd., oil-soluble azo polymerization initiator) was injected into the flask, and immediately, a dye having the following composition was used. The solution 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 Deionized water: 97 parts by weight n-butoxymethylacrylamide: 5 parts by weight

(Dye solution) n-butoxymethylacrylamide: 29 parts by weight Glycidyl methacrylate: 15 parts by weight Divinyl adipate: 1 part by weight Orazole Red G (manufactured by Ciba Specialty Chemicals, metal complex of red azo dye): 12 0.5 parts by weight Ion exchange water: 50 parts by weight Sodium dodecyl sulfate: 0.5 parts by weight V-65 (manufactured by Wako Pure Chemical Industries, oil-soluble azo polymerization initiator): 1 part by weight

The obtained colored fine particle emulsion D100
0.1 parts by weight of γ-aminopropyltrimethoxysilane and 0.2 parts by weight of 1,2-propanediamine are diluted with 10 times the amount of ion-exchanged water and added while stirring at room temperature, and coloring is performed. A fine particle emulsion was obtained.

[0164] The obtained colored fine particle emulsion was treated with a pore size of 1
After filtration through a μm filter, 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.).
It was 0 nm.

Comparative Example 6 The colored fine particle emulsion obtained in Comparative Example 4 was subjected to the following printing properties.
It was subjected to resolubility evaluation.

Comparative Example 7 0.2 parts by weight of N-β (aminoethyl) γ-aminopropyltrimethoxysilane was diluted with 10 parts by weight of ion-exchanged water in 100 parts by weight of the colored fine particle emulsion obtained in Comparative Example 4, and the mixture was cooled to room temperature. It was added while stirring under the conditions to obtain a colored fine particle emulsion.

[Evaluation of printability] The colored 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 used as a piezo ink jet printer (trade name: PM-750C; A printing test was performed on A4 size paper using a printer manufactured by Seiko Epson Corporation. The results are shown in Table 4.

(Composition of ink for evaluation) Colored fine particle emulsion: 25 parts by weight Glycerin: 25 parts by weight Ion-exchange water: solid content of colored fine particle emulsion is 10
Add the required amount to give the weight%.

[0169]

[Table 4]

Evaluation of printing stability and ink rectilinearity in Table 4 was performed based on the following criteria. Printing stability ：: A4 10 sheets can be printed stably. C: A4 clogging of nozzles occurs when 2 or more sheets and 10 sheets or less. ×: clogging of the nozzle occurs with two or less A4 sheets. Ink straightness ：: Ink is ejected from the nozzle in a hanging direction. X: Ink is ejected from the nozzle obliquely.

Example 16 1 g of ammonium persulfate was added to 100 g of the colored fine particle emulsion obtained in Example 1 to prepare a colored fine particle emulsion for an electrodeposition color filter, and a glass plate coated with ITO and a platinum electrode were subjected to electrodeposition. It was immersed in the 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 μm.

Example 17 2 parts by weight of sodium dodecyl sulfate (trade name "New Frontier S510", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), 194 parts by weight of deionized water and 10 parts by weight of n-butoxymethylacrylamide were separable. The solution was charged in a flask, and the temperature of the solution was raised to 50 ° C. while stirring under a nitrogen stream. Next, an ethanol solution 1 containing 0.5 parts by weight of an oil-soluble azo polymerization initiator (trade name “V-70”, manufactured by Wako Pure Chemical Industries, Ltd.)
0 parts by weight were added, and immediately, 89 parts by weight of n-butoxymethylacrylamide, 1 part by weight of ethylene glycol dimethacrylate and a metal complex of a red azo dye (trade name "Orazol Red G", manufactured by Ciba Specialty Chemicals) ) 2 parts by weight of a dye solution
It was dropped over time. Thereafter, a polymerization reaction was carried out at the same temperature for 3 hours, and then cooled to room temperature to prepare a colored fine particle emulsion.

The obtained emulsion of colored fine particles was prepared by
After filtering through a μm filter, a laser light scattering particle size distribution analyzer (Microtrack, Nikkiso Co., Ltd.)
The average particle diameter was 94 nm when the particle diameter of the colored fine particles was measured by using.

Next, the glass and platinum electrodes coated with ITO 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 electrodes. The thickness of the obtained color filter layer was 1.4 μm.

Comparative Example 8 50 parts by weight of n-butoxymethylacrylamide, 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, replaced with nitrogen, and then oil-soluble. 100 parts by weight of an ethanol solution containing 10 parts by weight of an azo polymerization initiator (trade name "V-65", manufactured by Wako Pure Chemical Industries, Ltd.)
The polymerization reaction was performed while dropping over time. Thereafter, the polymerization reaction was continued at the same temperature for 3 hours. Next, 20 parts by weight of a water-soluble dye was added as a coloring agent, dissolved and then cooled to room temperature, and 600 parts by weight of water (aqueous solvent) containing 1 part by weight of ammonia water was added as a pH adjuster. A colored resin aqueous solution was prepared.

Next, the colored resin aqueous solution 1 obtained above
1 part by weight of ammonium persulfate was added to 00 parts by weight, and 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 the obtained color filter layer was 1.9 μm.
m.

[Evaluation of Adhesion] The ink jet printing inks of Examples 13 to 17 and Comparative Examples 6 to 8 were applied to a glass plate by 2 μm.
After casting at a thickness of 100 m and drying at 100 ° C. for 1 hour, a cross cut of 2 mm square was applied to the coating film. The test piece was further subjected to a heating test at 250 ° C. for 1 hour, and then a peeling test was performed with an adhesive tape, and the peeling state of the cross cut portion was visually checked. Table 5 shows the results.

[0178]

[Table 5]

<Evaluation of Color Filter> The haze of the color filters obtained in Example 17 and Comparative Example 8 and the resolubility of the electrodeposited film were evaluated. The results are shown in Table 6. The haze was evaluated with a haze 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.

[0180]

[Table 6]

[0181]

According to the present invention, since the above-mentioned constitution is employed, the color fine particles and the color fine particle emulsion having high color density and excellent stability against impacts and the like, and ink jet printing without clogging of nozzles because of resolubility. To provide a color filter for a liquid crystal display having excellent adhesion to ink and glass, and excellent transparency, and a colored fine particle emulsion for an electrodeposition color filter which can simplify the process because the electrodeposited film is not redissolved. Can be.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 265/10 C08F 265/10 4J100 C08K 3/00 C08K 3/00 C08L 33/24 C08L 33/24 C09B 67 / 02 C09B 67/02 A 67/26 67/26 A 67/40 67/40 C09D 11/00 C09D 11/00 G02B 5/20 101 G02B 5/20 101 (31) Priority claim number Japanese Patent Application No. 2000-237184 (P2000-237184) (32) Priority date August 4, 2000 (2000.8.4) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 2000-242820 (P2000- (242820) (32) Priority Date August 10, 2000 (August 2000) (33) Priority Country Japan (JP) (72) Inventor Yoshiyuki Oguchi 2-1 Momoyama, Shimamoto-cho, Mishima-gun, Osaka Prefecture Sekisui Chemical Co., Ltd. F-term (reference) 2H048 BA4 7 BA57 BA62 BA64 4J002 BD051 BD141 BF021 BG041 BG051 BG061 BG071 BG101 BG121 BG131 CD191 DD056 DE196 EV186 EV256 EV296 FD116 GP00 GQ00 HA07 4J011 KA04 KA06 KA10 KA23 kb23 KB19 BA10 BA20 BA25 BA27 BA28 BA31 BA34 BA35 BA40 CA10 DA04 DA07 DA12 DA14 DA15 DA19 DB04 DB08 DB12 DB14 DB15 DB24 EA04 FA04 FA09 GA01 GA02 GA06 GA08 GA09 4J039 AD12 AF07 BC06 BC07 BC10 BC11 BC13 BC14 BC15 BC50 BC54 BC57 BE01 BE07 BE22 BE24 CA06 4J100 AB02S AC03S AC04S AG04S AL03S AL08T AL09S AL10R AL10T AM02S AM15S AM21P AM21Q AQ12R BA04P BA08T BA32Q BC53T CA04 CA05 CA06 EA07 FA03 FA20 JA07 JA32 JA43 JA45

Claims (15)

[Claims] 1. 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 comprises: The following general formula (I): (Wherein, R ¹ represents a hydrogen atom or a methyl group;
² represents an alkyl group having 3 to 6 carbon atoms) in an amount of 10% by weight or more, and the colored fine particles have at least a cross-linked structure formed on the surface thereof. A colored fine particle emulsion characterized by the above-mentioned. 2. The colored fine particle emulsion 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): (Wherein, R ³ represents a hydrogen atom or a methyl group, and R ⁴ ,
R ⁵ and R ⁶ are each independently a C 1-8 alkyl group, a C 1-8 aralkyl group or a C 7-1
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 colored fine particle emulsion according to claim 1, which is a salt obtained by reacting with a body. 4. The crosslinked structure has a molecular weight between crosslinks of 500.
The colored fine particle emulsion according to claim 1, 2 or 3, wherein the value is 0 or less. 5. The monomer composition according to claim 1, wherein the monomer composition contains a monomer having two or more vinyl groups.
5. The colored fine particle emulsion according to 2, 3 or 4. 6. The colored fine particles are 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, and further adding a crosslinking agent to the fine particles. Claims 1, 2, and 3 characterized by reacting
Or the colored fine particle emulsion according to item 4. 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. And then polymerizing the monomer having two or more vinyl groups.
Or a colored fine particle emulsion according to 6. 8. A colored fine particle is obtained by polymerizing a colored composition comprising a monomer composition and a coloring agent, and a monomer having a glass transition point of a homopolymer of 50 ° C. or higher and an oil-soluble polymer. 7. The method according to claim 1, wherein the monomer having a glass transition point of 50 ° C. or higher is polymerized after absorbing the initiator. Colored particulate emulsion. 9. The monomer composition according to claim 1, wherein the monomer composition contains 1 to 60% by weight of a vinyl monomer having an epoxy group. Or a colored fine particle emulsion according to 8. 10. A monomer composition comprising vinyl pyridine and 1
3. The composition according to claim 1, wherein
3. The colored fine particle emulsion according to 3, 4, 5, 6, 7, 8 or 9. 11. The colored fine particle emulsion according to claim 9, further comprising an amine silane coupling agent. 12. The method of claim 1, 2, 3, 4, 5, 6, 7,
An ink for inkjet printing, comprising the colored fine particle emulsion according to 8, 9, 10 or 11, and a humectant. 13. A color filter for a liquid crystal display, comprising the ink for inkjet printing according to claim 12. 14. The method of claim 1, 2, 3, 4, 5, 6, 7,
A colored fine particle emulsion for an electrodeposition color filter, comprising the colored fine particle emulsion according to 8, 9, 10 or 11, and an electrolyte. 15. The method of claim 1, 2, 3, 4, 5, 6, 7,
A colored fine particle obtained from the colored fine particle emulsion according to 8, 9, 10 or 11.