JP2001207007A - Colored resin emulsion composition, ink-jet ink and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous colored resin emulsion composition which is excellent in durability and color vividness and has a low viscosity, an ink-jet ink obtained by using the colored resin emulsion composition, and a color. Provide a filter. SOLUTION: A colored resin emulsion composition obtained by dispersing fine resin particles containing an oil-soluble dye and an organic pigment in an aqueous medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored resin emulsion composition having high color density, excellent transparency and durability, an ink jet ink and a color filter obtained from the colored resin emulsion composition.

[0002]

2. Description of the Related Art An emulsion in which colored fine particles are dispersed,
It is used for various purposes such as writing implement ink, printing ink, ink jet recording ink, paint, color filter, and the like, and it is necessary to maintain clear colors for a long period of time in the obtained printed matter. Therefore, the colored fine particles are
There is a need for optical properties containing a coloring agent such as a dye in a high concentration and high durability such as heat resistance, light resistance, solvent resistance and water resistance.

[0003] One type of conventionally known method for producing colored fine particles is, for example, vinyl chloride alone or
Emulsion polymerization of vinyl chloride and a monomer copolymerizable with vinyl chloride, or, to produce polymer fine particles using suspension polymerization,
There is known a method of producing colored fine particles by performing dyeing using a dye and a dyeing assistant. However, with this method, it was difficult to produce colored fine particles having high optical properties and high durability containing a dye in a high concentration.

Japanese Patent Publication No. 52-29336 discloses one or more unsaturated monomers containing butoxymethylacrylamide and one unsaturated monomer containing vinyl chloride, styrene and the like. Or when performing copolymerization with two or more, after dissolving or dispersing the dye in the unsaturated monomer,
A method is disclosed in which the unsaturated monomer is copolymerized to produce colored fine particles in which the interior is colored with a dye.

[0005] However, the colored fine particles obtained by this method do not contain a dye at a sufficiently high concentration and uniformity, and do not have sufficient optical properties and durability. In order to obtain colored fine particles having a high color density, the dye must have high solubility in the monomer composition. Therefore, it is necessary to select a monomer composition that can be uniformly dissolved at a high concentration even in the case of a mixture of dyes having completely different chemical structures. However, JP-B-52-29336 does not consider such a monomer composition. .

[0006] Colorants generally require durability. Since dyes are inferior to pigments in durability such as weather resistance and heat resistance, a colored resin emulsion having sufficiently satisfactory durability has not been obtained at present. On the other hand, pigments are inferior in transparency but inferior in transparency, and therefore are inferior to dyes in vividness of coloring. In addition, an ink consisting of only a pigment has a weak fixing power of the pigment to a base material. To solve this problem, a method of adding a water-soluble resin binder is employed, but in this case, the viscosity of the ink increases due to the resin binder. However, it becomes unsuitable for inkjet ink.

[0007]

SUMMARY OF THE INVENTION In view of the above, the present invention provides an aqueous colored resin emulsion composition which is excellent in durability and color vividness and has a low viscosity. It is an object of the present invention to provide an inkjet ink and a color filter that can be used.

[0008]

SUMMARY OF THE INVENTION The present invention is a colored resin emulsion composition obtained by dispersing resin fine particles containing an oil-soluble dye and an organic pigment in an aqueous medium. Hereinafter, the present invention will be described in detail.

The resin constituting the resin fine particles containing the oil-soluble dye used in the present invention is not particularly limited, and examples thereof include a vinyl resin obtained by addition polymerization, a urethane resin obtained by polyaddition, and a polyester resin obtained by polycondensation. Can be

In particular, the resin fine particles containing the oil-soluble dye are a single monomer of the oil-soluble dye and a monomer represented by the following general formula (I) (hereinafter referred to as a polymerizable monomer (I)). 30 in the body
It is preferable to use a resin obtained by polymerizing a monomer composition containing at least% by weight.

[0011]

Embedded image

In the above 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. R ² represents an alkyl group having 3 to 6 carbon atoms. As R ² , for example, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t
-Butyl group and the like.

When the content of the polymerizable monomer (I) is less than 30% by weight, it may be difficult to dissolve the oil-soluble dye at a high concentration in the monomer composition. The monomer composition may be composed of the polymerizable monomer (I) alone, or may be a mixture with another polymerizable monomer.

The other polymerizable monomer is not particularly limited as long as it is copolymerizable with the polymerizable monomer (I) and can dissolve the oil-soluble dye.
For example, vinyl monomers and the like are preferably used. The vinyl monomer is not particularly limited and includes, for example, vinyl chloride, vinyl acetate, styrene, vinylidene chloride, acrylonitrile, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, methacrylamide, glycidyl. Vinyl monomers having one polymerizable unsaturated bond in one molecule, such as methacrylate, polyethylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate;
2 per molecule of ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythrit tetraacrylate, allyl methacrylate, vinyl methacrylate, glycerol dimethacrylate, divinylbenzene, triallyl isocyanurate, divinyl adipate, etc. And vinyl monomers having at least two polymerizable unsaturated bonds. These vinyl monomers may be used alone or in combination of two or more.

The amount of the other polymerizable monomer is preferably less than 70% by weight of the total monomer composition. When the other polymerizable monomer is a polymerizable monomer having one polymerizable unsaturated bond in one molecule, the content is more preferably 30% by weight or less, and further preferably 5% by weight or less. When the other polymerizable monomer is a polymerizable monomer having two or more polymerizable unsaturated bonds in one molecule, the content is more preferably 0.1 to 10% by weight, and more preferably 0.5 to 10% by weight. -5% by weight is more preferred. When the amount of the polymerizable monomer having two or more polymerizable unsaturated bonds in one molecule is less than 0.1% by weight, the crosslinking resistance is insufficient and the resulting resin fine particles have poor solvent resistance and mechanical strength. In addition to being sufficient, the effect of fixing the dye in the resin fine particles cannot be expected so much. When the amount exceeds 10% by weight, not only the solubility of the dye is reduced, but also the aggregation of the resin fine particles, the precipitation of the dye and the like are liable to occur.

The oil-soluble dye used in the colored resin emulsion composition of the present invention preferably has a solubility in an organic solvent at 20 ° C. of 1% by weight or more. 20 ° C
Is less than 1% by weight, it is difficult to be included in the resin fine particles as described above. More preferably, the solubility in an organic solvent at 20 ° C. is 1% by weight.
As described above, 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 or less. The organic solvent is not particularly restricted but includes, for example, hydrocarbons, halogenated hydrocarbons, ketones, esters, alcohols, amides and the like.

The solubility in the 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 1%.
Examples of the oil-soluble dyes of 0% by weight or less include, for example, azo dyes, anthraquinone dyes, phthalocyanine dyes, triphenylmethane dyes, azo metal complex dyes, salts of anionic dyes and cationic monomers, Salts of an anionic dye and a cationic dye, etc .; solvent blue 44, 45,
Solvent red 24, 68, 8;
9, 124; solvent yellow 13, 1
4, 33, 79, 93; va blue 1, 6; va
t yellow6 and the like. Of these, salts of azo metal complex dyes or anionic dyes with cationic monomers are preferred. These may be used alone or in combination of two or more.

The cationic monomer is not particularly limited as long as it reacts with an anionic dye to form a salt. However, since it has high compatibility with the polymerizable monomer (I), the following general monomer is used. The cationic monomer represented by the formula (II) is preferred.

[0019]

Embedded image

In the formula, R ³ represents a hydrogen atom or a methyl group. Therefore, the monomer composition is an acrylamide derivative or a methacrylamide derivative. R ⁴ , R
⁵ and R ⁶ are the same or different and represent an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 6 to 10 carbon atoms or a cycloalkyl group. Examples of R ⁴ , R ⁵ , and R ⁶ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a benzyl group, a cyclohexyl group, and the like.
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.

Examples of the combination of the groups represented by R ⁴ , R ⁵ and R ⁶ include a methyl group, a methyl group and a benzyl group, 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 hydrophilicity is so strong that a reaction with an anionic dye may produce a hydrophobic salt. It becomes difficult. The cationic monomer represented by the general formula (II) has relatively strong hydrophobicity, and can precipitate a salt by reacting with the anionic dye.

Further, the cationic monomer represented by the above general formula (II) and the monomer composition are copolymerized, whereby the oil-soluble dye is fixed to the resulting polymer, and the oil-soluble dye is fixed. Can be suppressed.

The amount of the oil-soluble dye is preferably 1 to 50 parts by weight, and more preferably 5 to 50 parts by weight, based on 100 parts by weight of the monomer composition.
-30 parts by weight are more preferred. If the amount is more than 50 parts by weight, the concentration of the dye composition will be too high, and it will not only be difficult to add the dye composition, but also the dye may be separated during polymerization.

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

The method for producing the resin fine particles containing the oil-soluble dye is not particularly limited. Emulsion polymerization, suspension polymerization, soap-free polymerization, dispersion polymerization, General emulsion preparation methods such as phase inversion emulsification can be mentioned. Above all, from the viewpoint of easy particle size control and production efficiency, a method of obtaining resin fine particles by emulsion polymerization of the vinyl monomer composition as described above is preferable.

When the resin fine particles containing the oil-soluble dye are produced by emulsion polymerization, the monomer composition and the oil-soluble dye are subjected to emulsion polymerization in the presence of a polymerization initiator and an emulsifier. The polymerization initiator is not particularly limited, and includes, for example, an oil-soluble or water-soluble organic azo compound, an inorganic peroxide such as potassium persulfate, ammonium persulfate, an organic peroxide, the inorganic peroxide and a sulfite, and the like. Redox compositions in combination with the above reducing agents. Among these, an organic azo compound is preferable, and an organic azo compound having a half-life of 10 hours and a decomposition temperature of 40 to 80 ° C is more preferable.

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

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

The emulsifier is not particularly restricted but includes, for example, anionic, cationic or nonionic surfactants. Among these, cationic surfactants are not very dispersible, and nonionic surfactants tend to increase the particle size of resin fine particles containing oil-soluble dyes in the obtained colored resin emulsion. Therefore, anionic surfactants are preferred.

Examples of the above anionic surfactant include alkyl sulfates such as sodium alkyl sulfate and ammonium alkyl sulfate; and alkyl sulfonates such as sodium alkyl sulfonate and ammonium alkyl sulfonate. These may be used alone or in combination of two or more.

Further, as the anionic surfactant, those containing a polymerizable group can be suitably used. Examples of the surfactant having an anionic polymerizable group include sulfonic acid (salt) type and carboxylic acid (salt)
Type, phosphate ester (type) and the like. Above all,
Phosphate esters having a polymerizable unsaturated bond are preferred because they have the advantage of not affecting the physical properties of the coating film because they are fixed to the resin fine particles.

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.

In the case of producing fine resin particles containing an oil-soluble dye by emulsion polymerization, the reaction conditions are appropriately determined according to the types of the monomer composition, the oil-soluble dye, the polymerization initiator, the emulsifier, etc. to be used. For example, a monomer composition containing the polymerizable monomer (I), an emulsifier, and deionized water are charged into a flask, and the temperature is adjusted while stirring the emulsifier aqueous solution under a nitrogen stream. After the temperature was raised to the reaction temperature, a solution of the polymerization initiator was poured into the flask, a dye solution containing an oil-soluble dye was added dropwise over 1 to 2 hours, and further stirred at the same temperature for 3 to 4 hours. By performing emulsion polymerization using a method such as cooling to room temperature, a colored resin emulsion composed of resin fine particles containing an oil-soluble dye can be produced.

The amount of the polymerization initiator is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the monomer composition.
More preferably, it is 0.2 to 5 parts by weight. The concentration of the emulsifier is not particularly limited, but is preferably 0.5 to 10% by weight. The amount of the emulsifier is not particularly limited,
The weight ratio of the dye solution to the aqueous solution of the emulsifier is 1/5 to 1/1 /
1 is preferred. The reaction temperature is not particularly limited, but is usually preferably 10 to 100 ° C. More preferably, 40
８０80 ° C.

Since the resin fine particles containing the oil-soluble dye used in the colored resin emulsion composition of the present invention have the above-mentioned constitution, they contain the dye in a high concentration. In particular, when a salt obtained by reacting an anionic dye and a cationic monomer is used as the oil-soluble dye,
Since the cationic monomer is incorporated in the copolymer, the anionic dye is firmly fixed in the fine particles of the copolymer by ionic bonding.

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

The colored resin emulsion composition of the present invention comprises:
It is obtained by mixing an aqueous dispersion in which an organic pigment is dispersed in an aqueous medium, with a colored resin emulsion in which resin fine particles containing an oil-soluble dye are dispersed in an aqueous medium. The aqueous dispersion of the organic pigment is obtained by pulverizing the organic pigment with a ball mill or the like in the presence of water and a dispersant. The particle size of the organic pigment is preferably 0.5 μm or less, more preferably 0.2 μm or less. The ionicity of the dispersant used for the organic pigment is preferably the same as that of the emulsifier used for the fine resin particles, and more preferably anionic. As the organic pigment, for example, in terms of a color index number, pigment Red
139, 177; pigment yellow 11
7, 129, 139, 150, 185; pigment
blue 6,60; pigment black
6 and the like.

The colored resin emulsion composition of the present invention comprises:
As described above, fine particles containing a dye in a high concentration are dispersed, so that the color density is high, and since a dye and a pigment are used, transparency and durability, particularly both heat resistance and light resistance are improved. Are better.

The colored resin emulsion composition of the present invention comprises
By adding a humectant such as glycerin or ethylene glycol, or a surfactant, an inkjet ink excellent in optical properties and durability in which fine particles containing a dye are dispersed at a high concentration can be obtained. An inkjet ink produced by adding a humectant as an essential component to the colored resin emulsion composition of the present invention is also one of the present invention.

Further, a plurality of types of colored resin emulsion compositions containing dyes of different colors are applied to predetermined sections on a transparent substrate, respectively, and then subjected to a heat treatment, whereby a color used in a liquid crystal display device or the like is obtained. The filter can be suitably formed. Alternatively, a color filter can be formed by printing an inkjet ink having three primary colors of red, green, and blue or complementary colors of cyan, magenta, and yellow on a substrate. A color filter produced using the colored resin emulsion composition of the present invention or the inkjet ink of the present invention is also one of the present invention.

[0042]

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, New Frontier
S510 (Daiichi Kogyo Seiyaku Co., Ltd.) 4 parts by weight, deionized water 1
94 parts by weight and n-butoxymethylacrylamide
Charge 10 parts by weight into a flask and stir under a nitrogen stream.
Meanwhile, the liquid temperature was raised to 50 ° C. Next, V-70 (Wako Jun
Includes 0.5 parts by weight of an oil-soluble azo polymerization initiator manufactured by Yakusha
Inject 10 parts by weight of the ethanol solution into the flask and immediately
Then, a dye solution having the following composition is added dropwise over 2 hours.
Was.Composition of dye solution  89 parts by weight of n-butoxymethylacrylamide 1 part by weight of ethylene glycol dimethacrylate 20 parts by weight of vinyl vinyl GLS (manufactured by Clariant, blue dye)

After stirring at the same temperature for 3 hours, the mixture was cooled to room temperature to obtain a colored resin emulsion A. To 100 parts by weight of the obtained colored resin emulsion A was added 50 parts by weight of a blue pigment dispersion Hostafine Blue B2G (manufactured by Clariant), and the mixture was further stirred for 1 hour to obtain a colored resin emulsion composition.

The obtained colored resin emulsion composition was
After filtration through a filter having a pore size of 1 μm, 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.), and the average particle size was 127 nm. .

The obtained colored resin emulsion composition
Inkjet dischargeability and lightfastness by the method shown below
Properties and heat resistance were evaluated. The results are shown in Table 1.Evaluation method  (Inkjet ejection property) The obtained colored resin emulsion
Ink composition with the inkjet ink in the following formulation
And a piezo-type inkjet printer (trade name: PM
-750C, manufactured by Seiko Epson Corporation)
went.Composition of evaluation ink  Colored resin emulsion composition 25 parts by weight Glycerin 25 parts by weight Deionized water 50 parts by weight

(Light resistance) The obtained colored resin emulsion composition was cast to a thickness of 1 μm on a 1.2 mm glass substrate by a spin coater, and irradiated with a 750 W high-pressure mercury lamp from a distance of 50 cm for 10 hours. Then, a change in color was evaluated by a color difference (ΔE).

(Heat resistance) The obtained colored resin emulsion composition was cast on a 1.2 mm glass substrate to a thickness of 1 μm with a spin coater, and heated at 230 ° C. for 1 hour.
The change in color was evaluated by a color difference (ΔE).

Example 2 In the composition of the dye solution, Orasol Red G (manufactured by Ciba Geigy, a metal complex of a red azo dye) was used instead of Savinyl Blue GLS.
Example 1 except that Hosta Fine Red 2BLSE (manufactured by Clariant, red dye) was used instead of G.
Synthesis was performed in the same manner as in the above to obtain a colored resin emulsion B. To 100 parts by weight of the obtained colored resin emulsion B, 50 parts by weight of a red pigment dispersion Hostafine Red HF3S (manufactured by Clariant) was added, and the mixture was further stirred for 1 hour to obtain a colored resin emulsion composition. The obtained colored resin emulsion composition is filtered through a filter having a pore size of 1 μm,
When the particle size of the colored resin was measured, the average particle size was 12
It was 0 nm. Moreover, about the obtained colored resin emulsion composition, the inkjet discharge property, the light resistance, and the heat resistance were evaluated similarly to Example 1. The results are shown in Table 1.

Comparative Example 1 The colored resin emulsion A obtained in Example 1 was used with a pore size of 1 μm.
When the particle diameter of the colored resin was measured by filtration with a filter of m, the average particle diameter was 92 nm. In addition, with respect to the colored resin emulsion A, the ink jet ejection property, light resistance, and heat resistance were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 The colored resin emulsion B obtained in Example 2 was used with a pore size of 1 μm.
When the particle diameter of the colored resin was measured by filtration with a filter of m, the average particle diameter was 92 nm. In addition, with respect to the colored resin emulsion B, the ink jet ejection property, light resistance, and heat resistance were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0052]

[Table 1]

From Table 1, it can be seen that the colored resin emulsion compositions obtained in Examples 1 and 2 showed little change in color both after light irradiation and after heating, and were excellent in both light resistance and heat resistance. On the other hand, the colored resin emulsions obtained in Comparative Examples 1 and 2 were not excellent in both light resistance and heat resistance.

[0054]

Since the colored resin emulsion composition of the present invention has the above-mentioned constitution, it has good color development and excellent light resistance and heat resistance. By using the colored resin emulsion composition of the present invention, it is possible to obtain an ink-jet ink and a color filter which are excellent in both light resistance and heat resistance and have good coloring.

Claims (4)

[Claims] 1. A colored resin emulsion composition comprising resin fine particles containing an oil-soluble dye and an organic pigment dispersed in an aqueous medium. 2. A resin fine particle containing an oil-soluble dye, comprising: a monomer composition containing the oil-soluble dye and a monomer represented by the following general formula (I) in an amount of 30% by weight or more of all monomers. The colored resin emulsion composition according to claim 1, comprising a resin obtained by polymerizing the resin. Embedded image In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² is
Represents an alkyl group having 3 to 6 carbon atoms. 3. An ink-jet ink comprising a coloring resin emulsion composition according to claim 1 and a humectant added as an essential component. 4. A color filter produced using the colored resin emulsion composition according to claim 1 or 2, or the inkjet ink according to claim 3.