JP2003261790A - Colored resin emulsion and method for producing the same, ink for ink jet printing, and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink which is used for ink jet printing and has excellent storage stability with time and an excellent ink jetting property, and to provide a color filter produced by using the ink for the ink jet printing. <P>SOLUTION: This colored resin emulsion is prepared by dispersing colored resin fine particles comprising a vinylic resin containing an organic pigment in an aqueous medium. The ink for the ink jet printing is prepared from the colored resin emulsion. The color filter is prepared from the ink for the ink jet printing. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a colored resin emulsion having excellent stability, a method for producing the same, an inkjet printing ink using the colored resin emulsion, and a color filter using the inkjet printing ink. .

[0002]

2. Description of the Related Art Various writing instrument inks, printing inks, ink-jet recording inks and various coating paints in which pigments are dispersed have been conventionally used because of their excellent light resistance, heat resistance and water resistance. There is. In recent years, this pigment-based ink has been favorably used for applications such as color filters for liquid crystal display devices. However, in a pigment-based color filter, the light transmitted through the color filter coating film is affected by the pigment particles dispersed in the coating film and scattered, resulting in a turbid color tone or a polarization degree of the transmitted light. There was a problem of disturbing and reducing the contrast. Since such a problem is caused by the fact that the particle diameter of the pigment particles in the coating film is not sufficiently small, the pigment used for the color filter needs to be very finely divided.

On the other hand, ink jet printing and painting are not only widely used as printers for personal computers because they can draw fine characters and patterns in a non-contact manner, but also printing, printing and drawing for various industries. Is used for. Of these, JP-A-11-2
As disclosed in Japanese Patent No. 1487, attempts to form a color filter of a liquid crystal display device by an inkjet method have been actively studied. The formation of the color filter by the inkjet method has an advantage that the productivity is superior to the conventional method in which the photo process is repeated for every three primary colors.

Generally, an ink jet ink having a low surface tension such as an organic solvent is difficult to stably eject the ink from a nozzle, and thus an aqueous ink is used. Therefore, in an inkjet ink using an organic pigment-based coloring material, a pigment dispersant is used to disperse the pigment in the aqueous medium. For example, Japanese Patent Laid-Open No. 11-2
Japanese Patent No. 1487 discloses a pigment-dispersed water-based ink in which a pigment is dispersed in an aqueous medium with a high molecular surfactant and a low-molecular anionic surfactant. On the other hand, for the color filter forming ink, it is necessary to form a transparent coating film colored in three primary colors on a glass substrate or the like, but the polymer dispersant and surfactant described above are themselves film-forming. Since it does not have a function, a resin component that plays the role of a binder was required separately.

Further, Japanese Patent Application Laid-Open No. 11-21487 discloses an ink in which an organic pigment and a binder resin dispersed in an aqueous medium by a polymer surfactant are added separately. However, the surfactant used for dispersing the organic pigment not only improves the dispersibility of the pigment, but also diffuses in the medium and adversely affects the physical properties of the ink itself. Such an adverse effect is, for example, that the surface tension of the ink is remarkably lowered, or that the interaction between the pigment particles and the binder resin is strengthened and the viscosity of the ink is increased. There is a problem that the dischargeability is impaired.

Further, an ink containing a large amount of a pigment dispersant necessary for pigment dispersion is not preferable because it causes agglomeration and viscosity increase with time when left at high temperature for a long time. Since the pigment used in the color filter has a sufficiently small particle size, it has a large specific surface area, and the problem due to such interaction becomes more remarkable. On the other hand, JP-A-200
Japanese Unexamined Patent Publication No. 0-239392 discloses colored resin fine particles whose stability is improved by pigment-containing resin fine particles in which a pigment coated with a self-emulsifying resin is dispersed in the resin. However, even in this method, the water-soluble resin is used for the purpose of temporarily dispersing the pigment in the aqueous medium and for stably dispersing the pigment in the formed self-emulsifying resin in the colored resin fine particles. Such a water-soluble resin as a pigment dispersant may not be completely incorporated into the resin fine particles, and similarly, the viscosity of the ink and the surface tension may be lowered.

In the use of ink for ink jet printing, which is easily affected by the physical properties (liquid physical properties) of the ink itself, the viscosity and surface tension are affected by such a component that is completely unrelated to the control of the ejection property of the ink jet. Is a major constraint in designing the ink composition, and it is technically extremely difficult to obtain an ink for inkjet printing that can eject the ink stably and is excellent in stability over time. there were.

[0008]

In view of the above, the present invention has been made.
An object of the present invention is to provide an ink for inkjet printing, which has excellent storage stability over time and an excellent ink jetting property, and a color filter manufactured using the ink for inkjet printing.

[0009]

The present invention is a colored resin emulsion in which colored resin fine particles made of a vinyl resin containing an organic pigment and having an average particle diameter of 50 to 500 nm are dispersed in an aqueous medium. The content of the organic pigment contained in 3 to 40 parts by weight with respect to 100 parts by weight of the vinyl resin.
It is a weight part, and the colored resin fine particles contain no pigment dispersant in the colored resin fine particles.

The present invention will be described in detail below. In the present invention, the vinyl resin is used as a resin binder. The resin binder in the present invention is a resin which itself has a film-forming property at room temperature, and is a resin which can form a uniform transparent coating film by film-forming.

The pigment dispersant in the present invention is a compound having a pigment dispersing function for dispersing a pigment in an aqueous medium or a resin binder, and having no film-forming property at room temperature. Specific examples include various low molecular weight surfactants, water-soluble polymer compounds having no film-forming property, and water-dispersible polymer compounds. The film-forming property in the present invention is a property of forming a coating film when the medium is volatilized. In the present invention, it is preferable to form a coating film as transparent as possible.

The vinyl resin used in the present invention comprises a monomer mixture comprising a hydrophobic vinyl monomer, an anionic group-containing vinyl monomer and a nonionic hydrophilic group-containing vinyl monomer. It is preferably a vinyl resin obtained by polymerization.

The hydrophobic vinyl monomer is a monomer having a solubility in water at 20 ° C. of 10% by weight or less, and a compound having at least one polymerizable double bond.
Examples of the hydrophobic vinyl-based monomer include methyl (meth) acrylate, ethyl (meth) acrylate,
n-Butyl (meth) acrylate, isobutyl (meth)
Acrylate, n-octyl (meth) acrylate, 2
-Ethylhexyl (meth) acrylate, n-dodecyl (meth) acrylate, stearyl (meth) acrylate, 2-chloroethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, methyl-α-chloro (meth) acrylate , (Meth) acrylic acid esters such as glycidyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate; acrylonitrile, methacrylonitrile; maleimides such as phenylmaleimide and cyclohexylmaleimide; vinyl acetate, vinyl valerate, vinyl versatate, etc. Fatty acid vinyl ester; vinyl ethers such as ethyl vinyl ether and butyl vinyl ether; vinyl halides such as vinyl chloride, vinylidene chloride and vinyl bromide; ethylene, propylene, - butene, 2-butene,
Butadiene; vinyl-based polymerizable monomers having one polymerizable unsaturated bond in one molecule of styrene derivatives such as styrene and α-methylstyrene. These hydrophobic vinyl monomers may be used alone or in combination of two or more kinds. The (meth) acrylate referred to in the present invention means acrylate or methacrylate.

The polymerizable monomer represented by the following general formula (1), which is the hydrophobic vinyl-based monomer, is contained in an amount of 10% by weight or more based on the monomer components constituting the vinyl-based resin. Preferably. CH ₂ = CR ¹ CONHCH ₂ OR ² ··· (1)

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

These hydrophobic (meth) acrylamide derivatives may be used alone or in combination of two or more kinds. Moreover, since the hydrophobicity is imparted by setting the carbon number of the alkyl group represented by R ² to 3 to 6,
It tends to exist inside the colored resin fine particles. Therefore, when it exists as an emulsion, unnecessary cross-linking reaction between particles is prevented, and the storage stability of the ink is improved.

Since the above-mentioned hydrophobic (meth) acrylamide derivative causes a crosslinking reaction by heating, it is possible to impart thermosetting property to the coating film of the obtained colored resin emulsion.

When the amount of the hydrophobic (meth) acrylamide derivative used is less than 10% by weight of the monomer components constituting the vinyl resin, the thermosetting property of the coating film of the colored resin emulsion is insufficient. As a result, solvent resistance, chemical resistance, and water resistance may become insufficient.

When the above hydrophobic (meth) acrylamide derivative is copolymerized in the vinyl resin, it acts as a potential cross-linking point in the resin. That is, the alkoxymethyl (meth) acrylamide groups derived from the hydrophobic (meth) acrylamide derivative in the resin undergo self-crosslinking when the alkoxymethyl (meth) acrylamide groups react with each other when heated to about 120 ° C or higher. By carrying out the radical polymerization reaction at a temperature lower than the above-mentioned crosslinking reaction, it is possible to suppress gelation during polymerization and increase in the molecular weight more than necessary and to obtain a stable emulsion.

Further, when a coating film printed with an ink comprising a colored resin emulsion containing the above-mentioned hydrophobic (meth) acrylamide derivative is baked, a strong crosslinked structure is formed and solvent resistance is imparted to the coating film. be able to. Therefore, when this ink is used as a color filter, solvent resistance and water resistance can be imparted to the coating film by this crosslinking reaction.

Further, the hydrophobic vinyl-based monomer (including the hydrophobic vinyl-based monomer composition) contains 2 in 1 molecule in order to impart crosslinkability to the resulting vinyl-based resin.
A vinyl-based crosslinkable monomer having at least one polymerizable unsaturated bond may be used.

Examples of the vinyl-based crosslinkable monomers include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and allylmeth. (Meth) acrylate, vinyl (meth) acrylate,
Glycerol di (meth) acrylate, divinylbenzene, triallyl isocyanurate, divinyl adipate and the like can be mentioned. These vinyl-based crosslinkable monomers may be used alone or in combination of two or more kinds.

The amount of the vinyl-based crosslinkable monomer used is not particularly limited, but is preferably 10% by weight or less of the monomer components constituting the vinyl-based resin, and more preferably. It is 5% by weight or less. If the proportion of the vinyl-based crosslinkable monomer in the monomer components constituting the vinyl-based resin exceeds 10% by weight, gelation may occur during radical polymerization, or the resin viscosity may become high, making it difficult to disperse in water. .

The vinyl monomer having an anionic group is not particularly limited, but examples thereof include acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, and the like. Α- or β-alkyl derivatives of fumaric acid, maleic acid, citraconic acid,
Unsaturated dicarboxylic acids such as itaconic acid; carboxylic acids having a polymerizable unsaturated bond such as mono-2- (meth) acryloyloxyethyl ester derivatives of these unsaturated dicarboxylic acids.

Specific examples of the mono-2- (meth) acryloyloxyethyl ester derivative of the above unsaturated dicarboxylic acid include, for example, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid and the like can be mentioned. Also, phosphoric acid having a polymerizable unsaturated bond such as vinyl phosphate, 2- (meth) acryloyloxyethyl phosphate, methacryloxyethyl phosphate; t-butylacrylamide sulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropane Sulfonic acid having a polymerizable unsaturated bond such as sulfonic acid can also be used.

As the vinyl monomer having an anionic group, so-called anionic reactive surfactants such as sulfuric acid ester of polyoxyethylene nonylpropenyl phenyl ether can be used. Asahi Denka Kogyo Co., Ltd. "Adeka Rear Soap SE-10"
N "," Adecaria Soap SE-20N "," Aqualon HS series "manufactured by Daiichi Kogyo Seiyaku Co.," Aqualon BC "
Series "," Eleminol JS- "manufactured by Sanyo Chemical Industry Co., Ltd.
2 ”and the like. Further, acid anhydrides having a polymerizable double bond such as maleic anhydride can be regarded as potentially having an anionic group, and thus can be used as a vinyl-based monomer having an anionic group. Is.

The vinyl monomer having an anionic group may be used alone or in combination of two or more kinds.
By fixing the anionic group on the colored resin fine particles, dispersion stability is imparted to the colored resin emulsion of the present invention.

The vinyl monomer having an anionic group may be subjected to a polymerization reaction in a state where its salt is formed. However, when a hydrophobic (meth) acrylamide derivative is used, the crosslinking reaction is promoted under acidic conditions,
It is also effective for the purpose of suppressing undesired gelation during the reaction that the vinyl monomer having an anionic group is converted into a salt-formed state and then subjected to a polymerization reaction.

The above-mentioned vinyl monomer having a nonionic hydrophilic group is a monomer which dissolves in water in an amount of 10% by weight or more,
Although not particularly limited, for example, 2-hydroxyethyl (meth) acrylate, 1,4-hydroxybutyl (meth) acrylate, (poly) caprolactone-modified hydroxyethyl (meth) acrylate, (poly) ethylene glycol (meth ) Acrylate, (poly) ethylene glycol (meth) acrylate terminal methyl ester, (poly) propylene glycol (meth) acrylate, (poly) propylene glycol (meth) acrylate terminal methyl ester, (meth) acrylamide,
Methylol (meth) acrylamide, allyl alcohol, glycerin monoallyl ether and the like can be mentioned. These vinyl-based monomers having a nonionic hydrophilic group may be used alone or in combination of two or more kinds.

The nonionic hydrophilic group may be reactive. Examples of such a monomer having a nonionic hydrophilic group include N-methylol (meth) acrylamide and N-methoxymethyl (meth).
Examples thereof include hydrophilic (meth) acrylamide derivatives such as acrylamide and N-ethoxymethyl (meth) acrylamide, and these may be used alone or in combination of two or more kinds. However, these hydrophilic (meta)
The acrylamide derivative must be used in distinction from the above hydrophobic (meth) acrylamide derivative.
These hydrophilic (meth) acrylamide derivatives are likely to be present on the surface of the resin fine particles and cross-linking between the resin fine particles is likely to cause particle aggregation, so that it is necessary to pay attention to the amount used.

The vinyl-based resin used in the present invention is 100 parts by weight of the hydrophobic vinyl-based monomer, 1 to 30 parts by weight of the vinyl-based monomer having the anionic group, and vinyl having the nonionic hydrophilic group. A copolymer obtained by polymerizing a monomer mixture composed of 1 to 55 parts by weight of the system monomer is preferable.

In the above monomer mixture, the amount of the vinyl monomer having an anionic group used is less than 1 part by weight, or the vinyl monomer having a nonionic hydrophilic group is used, relative to 100 parts by weight of the hydrophobic vinyl monomer. If the amount of the system monomer used is less than 1 part by weight, the hydrophilicity of the resulting vinyl resin will be poor, and the particle size will not be sufficiently small when dispersed in an aqueous medium, which in turn results in a colored resin emulsion. The mechanical stability and storage stability of the product are insufficient.

The amount of the vinyl monomer having an anionic group is more than 30 parts by weight based on 100 parts by weight of the hydrophobic vinyl monomer, or the vinyl monomer having a nonionic hydrophilic group is used. If the amount exceeds 55 parts by weight, the hydrophilicity of the resulting vinyl resin becomes too strong, and the resin fine particle size obtained when dispersed in an aqueous medium becomes too small, or the resin fine particles are not formed in the aqueous medium. Without being dissolved, the resulting colored resin emulsion has a high viscosity, which deteriorates the ejection property as an ink for inkjet printing, and the coating film of the colored resin emulsion has insufficient moisture resistance and water resistance.

As a polymerization method for obtaining a vinyl resin from the above-mentioned monomer mixture, any polymerization method such as bulk polymerization and solution polymerization can be adopted. However, an organic solvent is used as a solvent in the presence of a polymerization initiator. The solution polymerization method in which the polymerization is performed is preferable because the polymerization reaction can be easily controlled.

The above-mentioned organic solvent is not particularly limited, but is, for example, a hydrocarbon-based organic solvent such as hexane, heptane, cyclohexane and toluene; an ether-based organic solvent such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxane. Ester type organic solvents such as ethyl acetate and butyl acetate; ketone type organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone;
Alcohol-based organic solvents such as methanol, ethanol and isopropanol; dimethyl sulfoxide, N, N-dimethylformamide and the like. These organic solvents may be used alone or in combination of two or more kinds.

The solution polymerization may be carried out in the coexistence of a water-soluble or hydrophilic liquid compound used as a moisturizing agent which will be described later, and when the organic solvent is removed by means such as heating or reduced pressure after the polymerization. , Boiling point at atmospheric pressure is 100 ℃
It is preferred to use less than organic solvents. Also, 10
An organic solvent having a boiling point of 0 ° C. or higher is not preferable because water may be distilled off at the same time when it is removed. However, this does not apply when solution polymerization is performed in the coexistence of a compound used as a moisturizer.

The ratio of the organic solvent and the monomer mixture used is not particularly limited, but it is preferably 10 to 50 parts by weight of the monomer mixture with respect to 100 parts by weight of the organic solvent. If the amount of the monomer mixture used is less than 10 parts by weight with respect to 100 parts by weight of the organic solvent, the productivity may be deteriorated. Conversely, the amount of the monomer mixture used with respect to 100 parts by weight of the organic solvent is 50 parts by weight. When it exceeds, the viscosity of the resulting vinyl resin solution becomes too high, and it may be difficult to emulsify and disperse it in an aqueous medium.

The polymerization initiator is not particularly limited, but examples thereof include oil-soluble organic azo compounds, inorganic peroxides and organic peroxides.

Specific examples of the peroxide type polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetoacetate peroxide and acetylacetone peroxide; 1,1-bis ( t-butylperoxy) 3,3,5-trimethylcyclohexane, n
-Peroxyketals such as -butyl 4,4-bis (t-butylperoxy) valerate; hydroper such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide Oxides; Dialkyl peroxides such as di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide; acetyl peroxide, isobutyl peroxide, octanoyl peroxide, benzoyl peroxide, 2,4- Diacyl peroxides such as dichlorobenzoyl peroxide; diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate And peroxycarbonates such as diallylperoxycarbonate; peroxyesters such as t-butylperacetate, t-butylperoxypivalate, t-butylperoxybenzoate and cumylperoxyoctate. In addition, acetylcyclohexyl sulfonyl peroxide, di-t-butyl peroxyhexahydroterephthalate and the like can be mentioned.

Examples of the organic azo compound type polymerization initiator include, for example, 2,2'-azobis (4-methoxy-2,
4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-
1-Methylethyl) azo] formamide, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis [N -(2-propenyl)-
2-Methylpropionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2,
2'-azobis (N-cyclohexyl-2-methylpropionamide), dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2,4,
4-trimethylpentane), 1,1′-azobis (1-
Acetoxy-1-phenylethane) and the like.

Among the above polymerization initiators, those having a 10-hour half-life temperature of 10 to 100 ° C. are preferable, and 40 to 90 ° C. is more preferable. These polymerization initiators may be used alone or in combination of two or more kinds.

The amount of the above-mentioned polymerization initiator to be used is not particularly limited, but 0.1 to 10 parts by weight of the polymerization initiator is preferable to 100 parts by weight of the monomer mixture, and more preferably 0. .2 to 5 parts by weight. Monomer mixture 10
If the amount of the polymerization initiator used is less than 0.1 parts by weight based on 0 parts by weight, the molecular weight of the resulting vinyl resin may be too high, and conversely, the amount of the polymerization initiator based on 100 parts by weight of the monomer mixture may be increased. If the amount used exceeds 10 parts by weight, the molecular weight of the resulting vinyl resin binder may become too low.

The molecular weight of the vinyl resin used in the present invention is preferably 3,000 to 300,000, and more preferably 8.
It is 1,000 to 200,000. When the weight average molecular weight is less than 3,000,
The glass transition temperature (Tg) of the polymer constituting the obtained organic colored fine particles is too low, so that the water resistance and solvent resistance of the ink on the printed matter are poor, and a part of the resin becomes water-soluble to form resin particles. Otherwise, the viscosity of the ink becomes high, and as a result, the ink jet printability may deteriorate. On the other hand, when the molecular weight exceeds 300,000, the viscosity when dispersed in water is too high, the dispersion cannot be sufficiently performed, the resin particle size becomes large, and the storage stability when used as an ink may be poor. The molecular weight referred to here is the weight average molecular weight determined by gel permeation chromatography (GPC) by standard polystyrene conversion.

The glass transition temperature (T
As g), 20-100 degreeC is preferable. The Tg here is measured by a differential scanning calorimetry (DSC). If the Tg is less than 20 ° C, fusion between resin particles is likely to occur, which may impair the storage stability of the ink or cause nozzle clogging during inkjet printing. Further, when the temperature exceeds 100 ° C., the fusion of the ink coating film after printing becomes sufficiently difficult to occur, and particularly when it is used for printing a color filter which is mentioned as one usage mode of the present invention, It may cause turbidity and deteriorate the display quality of the liquid crystal screen.

The above-mentioned solution polymerization method and conditions may be appropriately set depending on the composition of the monomer mixture used, the type of the polymerization initiator and the like, and are not particularly limited. For example, a separable flask is used. A predetermined amount of each of the organic solvent and the mixed monomer is charged into a usual reaction container such as the above, the temperature is raised to the reaction temperature while stirring under a nitrogen stream, and then an organic solvent solution or dispersion of a polymerization initiator is added. The predetermined amount of 1
A desired vinyl resin solution can be obtained by carrying out a polymerization reaction while dropping for 2 hours, further continuing the polymerization reaction at the same temperature for 3 to 4 hours, and then cooling to room temperature. The reaction temperature is not particularly limited, but is preferably 10 to 100 ° C, more preferably 40.
~ 80 ° C.

In the present invention, various organic pigments are used as the coloring material. Since the pigment has excellent heat resistance and light resistance, when it is used for a color filter for a liquid crystal display, which is a main application of the present invention, it is exposed to a high temperature in a manufacturing process such as an overcoat or a thermosetting process of a sealing material. Therefore, it is preferably used for heat resistance or in applications requiring light resistance such as portable information terminals used outdoors.

The organic pigments used in the present invention include acidic dye lakes, basic dye lakes, azo pigments such as monoazo lake compounds, monoazo compounds, disazo compounds, condensed azo compounds and metal complex salt azo compounds; copper phthalocyanine compounds; Phthalocyanine pigments such as chlorinated copper phthalocyanine compounds and brominated copper phthalocyanine compounds;
Condensed polycyclic pigments such as anthraquinone compounds, thioindigo compounds, perinone compounds, perylene compounds, quinacridone compounds, dioxazine compounds, isoindolinone compounds, quinophthalone compounds, diketopyrrolopyrrole compounds; metal complex salts Examples include azomethine pigments.

These organic pigments are shown by color index: pigment red2, 3, 4, 5,
8, 9, 12, 14, 17, 22, 23, 31, 38,
48: 2, 48: 3, 48: 4, 53: 1, 57: 1,
83, 88, 112, 114, 122, 123, 14
4, 146, 147, 149, 168, 170, 17
5, 176, 177, 178, 179, 184, 18
5, 187, 188, 194, 202, 206, 20
7, 208, 209, 210, 214, 224, 24
2, 245, 247, 253, 254, 255, 25
6,257,262,263,264,266; pig
ment orange 5, 13, 16, 22, 34,
36, 38, 40, 43, 61, 62, 68, 69, 7
0, 71, 72, 74; pigment yellow
1, 3, 12, 13, 14, 16, 17, 24, 55,
73, 74, 75, 81, 83, 87, 95, 97, 1
08, 109, 110, 111, 117, 120, 12
6, 127, 129, 133, 138, 139, 15
1, 153, 154, 155, 167, 168, 16
9, 170, 172, 173, 174, 175, 17
6, 180, 181, 191, 192, 194, 19
6, 198; pigment blue 10, 15, 1
5: 1, 15: 2, 15: 3, 15: 4, 15: 6, 1
9, 56, 60, 61; pigment green
7, 36; pigment violet 19, 23,
32, 38, 50 and the like. These organic pigments may be used alone or in combination of two or more kinds.

Particles of the above organic pigment have a particle size of 50 to 300 nm.
It is preferable to use by atomizing to an average particle diameter of
More preferably, it is 50 to 200 nm. When the average particle size of the pigment exceeds 300 nm, it becomes difficult to make the average particle size of the obtained colored resin fine particles to be 500 nm or less, and when it is made into an ink, not only does it settle over time and the storage stability decreases, When it is used as an ink, it is not preferable because its ejection property is deteriorated.
Also, when used for color filter applications, if pigment particles with a large particle size are present in the coating film, the light passing through the filter is reduced by diffuse reflection, which reduces the brightness of the display or The depolarization reduces the contrast, which is not particularly preferable. On the other hand, if the average particle size of the pigment is less than 50 nm, the step of ultra-fine atomization becomes large, which is unnecessarily costly and not only industrially disadvantageous, but also heat resistance and light resistance are deteriorated, which is not preferable. .

The above-mentioned finely divided pigment is preferably dispersed as primary particles in the presence of water without the use of a pigment dispersant, or handled as a wet cake forming loosely bound secondary particles. The method for obtaining the wet cake is not particularly limited, but is, for example, JP-A-9-208.
No. 848, a precipitation method; an acid paste method, a salt milling method as described in JP-A-9-194773, and a wet milling method as described in JP-A-10-10312. A treatment in which a pigment dispersant is not used and the obtained slurry of finely divided pigment is washed and filtered to prepare a dispersion in which water is used as a medium. The pigment wet cake thus obtained may contain the binder resin used in the present invention.

As the colorant used in the present invention, an oil-soluble dye may be used in addition to the above organic pigment. The oil-soluble dye is excellent in heat resistance and light resistance as compared with a water-soluble dye, and thus can be used as a color filter. In addition, good solubility and encapsulation in organic solvents and vinyl resins are also one of the reasons why oil-soluble dyes are preferably used.

The oil-soluble dye is not particularly limited, but when the oil-soluble dye and the vinyl resin are mixed, the vinyl resin is mixed under the condition that the organic solvent solution of the vinyl resin is 20 ° C. It is preferable that 1 g or more of the oil-soluble dye is dissolved in 100 g of the solution, more preferably 1 g or more of the oil-soluble dye is dissolved in 100 g of the vinyl resin solution, and 1 part of the oil-soluble dye is dissolved in 100 g of water at 20 ° C.
g or less, 10 g or less in water at 100 ° C. Vinyl-based resin solution of oil-soluble dye at 20 ° C 10
If the amount dissolved with respect to 0 g is less than 1 g, the colorant may not be easily encapsulated in the resin fine particles.

The oil-soluble dye having such a dissolution property is not particularly limited, but for example, azo dyes, anthraquinone dyes, phthalocyanine dyes, triphenylmethane dyes, azo metal complex dyes, Examples thereof include rhodamine dyes. In terms of color index number, solvent blue25, 3
5, 36, 38, 44, 45, 59, 67, 70, 7
8, 104, 122, 124, 132; solvent
red3,8,18,24,27,49,52,6
8, 89, 124, 83, 83: 1, 84: 1, 89,
90: 1, 91, 92, 111, 122, 124, 12
5, 127, 130, 135, 143, 145, 14
6, 149, 150, 151, 179, 195, 21
4, 218, 225, 233; solvent yellow
low13,14,16,21,25,25: 1,3
3, 62, 79, 83, 83: 1, 88, 89, 93,
98, 114, 133, 157, 163; solven.
torange11, 40: 1, 41, 60, 62,
63, 99; solvent green3, 5, 2
8; solvent violet2, 13, 37, 4
9, 66; solvent black3, 7, 22,
22: 1, 27, 28, 29, 42, 43, 45; va
tblue1, 6; vatte yellow6 and the like. These oil-soluble dyes may be used alone or in combination of two or more.

The above oil-soluble dyes are preferably combined so that they can be uniformly mixed with the vinyl resin. That is, it is preferable to determine the organic solvent or the oil-soluble dye and the combination based on the affinity between the oil-soluble dye and the organic solvent or vinyl resin used.

The organic solvent used to dissolve both the oil-soluble dye and the vinyl resin is not particularly limited, but examples thereof include hydrocarbons, halogenated hydrocarbons and ketones. Examples thereof include esters, esters, alcohols, amides and the like. These organic solvents may be used alone or in combination of two or more kinds. Further, the organic solvent used to dissolve the oil-soluble dye,
It may be the same as or different from the organic solvent used for the solution polymerization of the monomer mixture.

As a method for producing the colored resin emulsion of the present invention, radical polymerization of the above-mentioned monomer mixture is carried out to obtain a vinyl resin, which is then added to an organic solvent solution of the vinyl resin,
Alternatively, if necessary, to a solution of an organic solvent in which both a vinyl resin and an oil-soluble dye are dissolved, a pigment wet cake made of an organic pigment and water and containing no pigment dispersant is added and uniformly mixed and dispersed to form a water-in-oil type. The first step of obtaining an emulsion,
A second step of adding an aqueous medium containing no pigment to the obtained water-in-oil emulsion to convert it into an oil-in-water emulsion, and a third step of removing the organic solvent by distillation to the outside of the system. And a so-called phase inversion emulsification method.

According to this phase inversion emulsification method, the hydrophilicity of the copolymerized anionic group and nonionic group imparts the vinyl resin itself with self-dispersibility in the aqueous medium. Disperses stably in an aqueous medium.
Therefore, since the colored resin emulsion of the present invention does not need to contain a large amount of a surfactant, the ink jetting property by the inkjet method is stable, and the coating film formed from the inkjet ink has water resistance and moisture resistance. Excel.

In the production method of the present invention, a pigment wet cake made of an organic pigment and water and containing no pigment dispersant is added to an organic solvent solution of a vinyl resin and mixed and dispersed uniformly by mechanical shearing force. In the step of obtaining the water-in-oil type emulsion, it is preferable to perform phase conversion (phase inversion) into the water-in-oil type emulsion after adding all the pigment wet cakes. Before adding all the pigment wet cake,
When the phase change occurs from the water-in-oil emulsion to the oil-in-water emulsion, the organic pigment in the pigment wet cake added after that will not be included in the vinyl resin, so the colored resin fine particles can be stably obtained. It is not preferable because it is not possible.

The content of the organic pigment in the pigment wet cake is preferably 5 to 25% by weight. Content rate is 5
If it is less than wt%, it will undergo phase conversion to an oil-in-water emulsion before adding all the pigment wet cakes as described above,
It is not preferable because pigment particles that are not included in the vinyl resin may be present. Further, if it exceeds 25% by weight, the fluidity of the wet cake is remarkably deteriorated, and it becomes difficult to uniformly mix and disperse it when mixing it with an organic solvent solution of a vinyl resin, which is not preferable.

The amount of the pigment wet cake added is preferably in the range of 3 to 40 parts by weight of the organic pigment in the pigment wet cake, more preferably 100 parts by weight of the vinyl resin in the vinyl resin solution. 5 to 35 parts by weight. When the amount of the organic pigment exceeds 40 parts by weight, it becomes difficult to encapsulate all the organic pigment particles in the vinyl resin, and it becomes impossible to obtain a stable emulsion. Further, even if all the pigment particles are included, the proportion of the vinyl-based resin contained in the total solid content becomes low, so that the vinyl-based resin hardly functions as a binder, and, for example, by drying the colored emulsion after discharging it. It is not preferable because it is difficult to obtain a colored coating film in which fine pigment particles are uniformly dispersed in the obtained coating film.

On the other hand, when the amount of the organic pigment is less than 3 parts by weight,
The pigment concentration in the obtained coating film is too low and the desired color density may not be obtained unless the coating film is made extremely thick, which is not preferable. When an oil-soluble dye is used in combination, the ratio of the organic pigment should be replaced with the total amount of the organic pigment and the oil-soluble dye.

When forming a coating film as a color filter, the required coating thickness and color density must be precisely controlled. The amount of the vinyl resin solution and the pigment wet cake may be determined so that

The organic solvent solution of the vinyl resin preferably has a viscosity of 1000 mPa · s or less at 20 ° C. when uniformly dispersed in the pigment wet cake. The viscosity of the organic solvent solution here is the viscosity of the solution including the oil-soluble dye when the oil-soluble dye is used. When the viscosity of the solution exceeds 1000 mPa · s, it becomes difficult to uniformly mix and disperse it with the pigment wet cake due to mechanical shearing force, which is not preferable.

The solution viscosity may be adjusted to some extent by adjusting the amount of the organic solvent. However, vinyl resin 1
The amount of organic solvent solution is 200 to 100 parts by weight.
It is preferably 0 part by weight. If it is less than 200 parts by weight, it is difficult to make the solution viscosity 1000 mPa · s or less, and if it exceeds 1000 parts by weight, the efficiency of distilling off the organic solvent in the final step is lowered, which is not preferable.

Further, in the production method of the present invention, the water-in-oil type emulsion obtained in the above step in the phase inversion emulsification operation is added with an aqueous medium containing no pigment to be converted into an oil-in-water type emulsion. It is preferable. The aqueous medium is preferably water alone, but if necessary,
It may be water to which one or more kinds of various additives such as a water-soluble organic solvent, a surfactant and an antifoaming agent are added.

Moisturizers described below may be used in part or in whole of the water-soluble organic solvent. Examples of the water-soluble organic solvent that can be used include water-soluble lower alcohols; water-soluble polyhydric alcohols such as ethylene glycol and glycerin; polyethylene glycols such as diethylene glycol and triethylene glycol; Alkyl ether or dialkyl ether; acetone and the like can be mentioned.

The addition amount of the aqueous medium used is not particularly limited, but the total amount of the water contained in the pigment wet cake and the aqueous medium added after the addition of the wet cake is a vinyl resin alone or a vinyl resin. The amount is preferably 50 to 300 parts by weight, and more preferably 50 to 200 parts by weight, based on 100 parts by weight of the organic solvent solution of the resin and the oil-soluble dye. If the amount of the aqueous medium is less than 50 parts by weight, the phase conversion into an oil-in-water type emulsion may not be achieved, and sufficient and stable emulsion dispersion may not be achieved. If the amount exceeds 200 parts by weight, the solid content of the obtained colored resin emulsion may be reduced. The concentration may become too low.

In the present invention, it is preferable to obtain an oil-in-water emulsion as described above and then add a basic compound to ionize the anionic groups of the vinyl resin. In the step of ionizing the anionic groups of the vinyl resin, the water-in-oil emulsion is added with an aqueous medium containing no pigment to convert it into an oil-in-water emulsion.
And the step of removing the organic solvent by distillation outside the system
It is preferable to carry out between the step and.

The basic compound used for such purpose is not particularly limited, but examples thereof include sodium hydroxide, sodium hydrogen carbonate, ammonia, trimethylamine, triethylamine, triethanolamine and the like. However, when used for forming a color filter, it is preferable to use an aqueous solution of ammonia, alkylamine or the like, because the presence of alkali metals may contaminate the liquid crystal to lower the specific resistance and lower the display image quality. . As described above, by converting the anionic group in the vinyl-based resin to the salt form, the hydrophilicity becomes stronger and a stable emulsion can be obtained.

In the production method of the present invention, the device for applying a mechanical shearing force used in the phase inversion emulsification method is not particularly limited, and for example, a rotor-stator type high speed such as a dissolver or a homogenizer. Stirrer by rotation; planetary stirrer that mixes by revolving the container at the same time as the rotation; sand mill, bead mill, ball mill,
Examples thereof include colloidal mills, paint shakers, static mixers, jet mixers, bubble homogenizers, ultrasonic homogenizers, and the like that disperse while applying mechanical shearing force.

In the production method of the present invention, after the phase conversion to the oil-in-water emulsion, the step of removing the organic solvent by distillation is carried out. The organic solvent can usually be partially or wholly removed by distillation by means such as heating or reduced pressure. It can also be removed by a continuous operation such as a thin film distillation apparatus.

The average particle size of the colored resin fine particles is 50 to 500 nm, preferably 50 to 200.
nm. If the average particle size exceeds 500 nm, the resin fine particles containing the colorant may settle over time in the case of a colored resin emulsion, and the particle size of the organic pigment should be less than 50 nm in order to reduce the particle size to less than 50 nm. However, this is not preferable because not only a very large-scale process is required for the ultrafine atomization of the pigment but also the heat resistance and light resistance of the pigment are deteriorated.

The relationship between the particle diameter of the obtained colored resin fine particles and the particle diameter of the organic pigment contained therein is such that the average particle diameter of the organic pigment is 10 to 80% of that of the colored resin fine particles.
Is preferable, and more preferably 20 to 60%. If it exceeds 80%, the organic pigment may not be completely encapsulated in the vinyl-based resin, the stability as colored resin fine particles may be reduced, and the stability of inkjet ejection may be impaired. Further, the vinyl-based resin becomes difficult to exhibit the function as a binder, and it becomes difficult to obtain a colored coating film in which fine pigment particles are uniformly dispersed in a coating film obtained by, for example, discharging an emulsion and then drying, which is not preferable. On the other hand, if it is less than 10%, the pigment concentration in the obtained coating film is too low, and the desired color density may not be obtained unless the coating film is made very thick.

The ink jet printing ink of the present invention comprises
A mixture of the colored resin emulsion and a moisturizer is used. In the above inkjet printing ink, the moisturizing agent can prevent the ink from drying in the inkjet nozzle by reducing the volatilization amount of the aqueous medium of the ink. It is possible to suppress the agglomeration, clogging of nozzles, etc., and to exhibit stable printing performance as an ink for inkjet printing. Further, it is possible to obtain an ink for inkjet printing which can promote smooth film formation of the obtained ink coating film and can form a coating film having good optical characteristics.

The moisturizer is not particularly limited as long as it is a water-soluble or hydrophilic liquid organic compound. Examples of such a compound include ethanol, n-propanol, 2-propanol, 1-butanol, 2-butanol, 1-heptanol, 2-heptanol, and 3-.
Heptanol, 1-hexanol, 1-octanol,
2-octanol, 1-nonanol, 1-decanol,
1-undecanol, 1-methoxy-2-propanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, 3,5,5-trimethyl-1hexanol,
2-ethyl-1-hexanol, cyclohexanol,
Monoalcohols such as 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, and benzyl alcohol; (di, tri, tetra)
Ethylene glycol, (di, tri, tetra) ethylene glycol monomethyl ether, (di, tri, tetra) ethylene glycol monoethyl ether, (di, tri, tetra) ethylene glycol monoisopropyl ether,
(Di, tri, tetra) ethylene glycol monopropyl ether, (di, tri, tetra) ethylene glycol monobutyl ether, (di, tri, tetra) ethylene glycol monoisobuty ether, (di, tri, tetra) ethylene glycol monohexyl Ether, (di, tri,
Tetra) ethylene glycol monophenyl ether,
(Di, tri, tetra) ethylene glycol monoallyl ether, (di, tri, tetra) ethylene glycol monoisoamyl ether, (di, tri, tetra) ethylene glycol dimethyl ether, (di, tri, tetra) ethylene glycol diethyl ether, ( Di, tri, tetra) ethylene glycol diisopropyl ether,
(Di, tri, tetra) ethylene glycol dipropyl ether, (di, tri, tetra) ethylene glycol monoacetate, (di, tri, tetra) ethylene glycol diacetate, (di, tri, tetra) ethylene glycol monomethyl ether acetate , (Di, tri, tetra) ethylene glycol monoisopropyl acetate,
(Di, tri, tetra) ethylene glycol monobutyl ether acetate and other (di, tri, tetra) ethylene glycol derivatives; polyethylene glycol or its derivatives;

(Di, tri, tetra) propylene glycol, (di, tri, tetra) propylene glycol monomethyl ether, (di, tri, tetra) propylene glycol monoethyl ether, (di, tri, tetra) propylene glycol monoisopropyl ether , (Di, tri, tetra) propylene glycol monopropyl ether, (di, tri, tetra) propylene glycol monobutyl ether, (di, tri, tetra) propylene glycol dimethyl ether, (di, tri, tetra) propylene glycol diethyl ether, ( Di, tri, tetra)
Propylene glycol monoacetate, (di, tri, tetra) propylene glycol diacetate, (di, tri, tetra) propylene glycol monomethyl ether acetate, and other (di, tri, tetra) propylene glycol derivatives; polypropylene glycol or its derivatives; 3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 3-hexene-2,5-diol, 1,5 -Pentanediol,
2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 2-butene-1,4-diol, neopentyl glycol and other diols, or their ether derivatives and acetate derivatives; glycerin, 1,
Polyhydric alcohols such as 2,4, -butanetriol, 1,2,6-hexanetriol, 1,2,5, -pentanetriol, trimethylolpropane, trimethylolethane, pentaerythritol, etc. or their ether derivatives, acetate derivatives Dimethyl sulfoxide, thiodiglycol, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, r-butyrolactone, 1,3-
Dimethyl-2-imidazolidine, sulfolane, formamide, N, N-dimethylformamide, N, N-diethylformamide, N-methylformamide, acetamide, N-methylacetamide, α-terpineol,
Examples thereof include ethylene carbonate, bropyrene carbonate, bis-β-hydroxyethyl sulfone, bis-β-hydroxyethyl urea, N, N-diethylethanolamine, abietinol and diacetone alcohol.

Among these compounds, the boiling point is 100
A water-soluble organic compound having a temperature of ℃ or more is preferable, for example, glycerin, (di, tri, tetra) ethylene glycol,
(Di, tri, tetra) ethylene glycol monoalkyl ether, dimethyl sulfoxide and the like are preferably used. These moisturizers may be used alone or in combination of two or more kinds.

The term "(di, tri, tetra) ethylene glycol" as used herein means diethylene glycol, triethylene glycol and tetraethylene glycol,
(Di, tri, tetra) propylene glycol means dipropylene glycol, tripropylene glycol and tetrapropylene glycol, respectively.

The amount of the humectant used is not particularly limited, but it is preferably 5 to 40% by weight in the ink for inkjet printing. If the amount of the moisturizer used in the ink for inkjet printing is less than 5% by weight, a sufficient moisturizing effect may not be obtained.
If it exceeds 0% by weight, the viscosity of the ink for inkjet printing may become too high, and it may take a long time to dry.

In the ink for ink jet printing, the solid content concentration of fine particles composed of a vinyl resin and a coloring agent is not particularly limited, but is 3 to 20% by weight.
Is preferred.

As the viscosity of the above ink jet printing ink, the viscosity (2
5 ° C.) is preferably 2 to 15 mPa · s, and more preferably 2 to 10 mPa · s. 2 mPa
If it is less than s, it may not be possible to stop the flow down from the ink nozzle, which may cause printing failure due to ink leakage. Further, when printing is performed on a glass substrate for a color filter, the film thickness may be uncontrollable due to excessive wetting and spreading on the glass substrate. 15 mP
When it exceeds a · s, the fluidity of the ink in the ink pipe of the printer is extremely deteriorated, which may result in defective printing due to insufficient ink supply to the nozzles. In addition, the air bubbles in the ink will not escape easily, and the air bubbles will entangle in the nozzles, making it difficult to print.

The above-mentioned ink jet printing includes a piezo method in which ink is ejected from a nozzle by vibration of a piezo element; a bubble jet (registered trademark) method in which ink is ejected by rapid heating of a heating element, and the like. The ink for use can be applied to any method.

The ink jet printing ink can be printed on paper or other medium by the ink jet printing printer for recording. It can also be printed on various substrates such as metal, plastic, and glass and used as a marking.

The color filter of the present invention can be manufactured using the above ink jet printing ink.
As the method for producing the color filter, the ink for inkjet printing is printed in a predetermined section on a transparent substrate such as glass or plastic by an inkjet printing method and then subjected to heat treatment, for example, a liquid crystal display device. A color filter used for the above can be suitably formed. Further, an inkjet printing ink using the colored resin emulsion of the present invention, which has three primary colors of red, green and blue and complementary colors such as cyan, magenta and yellow, is printed on a transparent substrate by an inkjet printing method. Also, the color filter can be preferably formed.

In particular, the ink for ink jet printing using the colored resin emulsion obtained by using the above-mentioned hydrophobic (meth) acrylamide derivative has the durability such as solvent resistance of the coating film by incorporating the reaction system of heat curing. Since it has improved properties, it is suitably used for color filters.

(Function) Since the colored resin emulsion of the present invention does not contain a pigment dispersant in the colored resin and is composed of colored resin fine particles having a sufficiently small particle size, the surface tension does not become too low and the viscosity is low. Since it does not become too high, it has excellent ejection stability when used as an ink for inkjet printing, and even when stored under high temperature for a long time, an ink having excellent storage stability without thickening or aggregation is obtained. be able to. Therefore, when a color filter is manufactured using the obtained inkjet ink, it is possible to accurately supply the ink to a predetermined section and to efficiently manufacture the color filter. Moreover, since an organic pigment is used as a colorant, a color filter having excellent heat resistance and light resistance can be obtained.

[0087]

BEST MODE FOR CARRYING OUT THE INVENTION The embodiments of the present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. In addition, "part" in the text means "part by weight". Further, water means ion-exchanged water.

Example 1 100 parts of n-butoxymethyl acrylamide, 1 of hydroxyethyl methacrylate
117.7 parts of a monomer mixture consisting of 1.8 parts and 5.9 parts of methacrylic acid was dissolved in 352.9 parts of ethyl acetate and charged in a separable flask, and after substituting with nitrogen, an oil-soluble azo-based polymerization was started. The polymerization reaction was carried out while dropping 11.8 parts of a 10 wt% ethanol solution of the agent (trade name "V-65", manufactured by Wako Pure Chemical Industries, Ltd.) over 1 hour. Further, after continuing the polymerization reaction at the same temperature for 3 hours, 6.9 parts of an azo metal oil-soluble dye (trade name “ORASOL Orange G”, manufactured by Ciba Specialty Chemicals) was dissolved.
Then, this was cooled to room temperature to obtain an organic solvent solution of the vinyl resin and the oil-soluble dye.

An anthraquinone-based red organic pigment (trade name "CROMOPH" is used while stirring at high speed an organic solvent solution of the vinyl resin and the oil-soluble dye using a homogenizer.
TAL Red A2B "(manufactured by Ciba Specialty Chemicals) is gradually added by a salt milling method to 92.7 parts of a pigment wet cake obtained by atomizing without using a pigment dispersant to obtain a water-in-oil emulsion. It was The pigment wet cake is composed of an organic pigment (content 15% by weight) and water and does not contain a pigment dispersant. The average particle size of the organic pigment was 95 nm as measured by a laser light scattering particle size distribution measuring device (device name “Microtrac”, manufactured by Nikkiso Co., Ltd.).

Thereafter, the above emulsion was further mixed with water 5
86 parts were added. It is considered that the viscosity was drastically lowered during the addition of the water, and thus the oil was converted into an oil-in-water type emulsion at this point. Subsequently, 120 parts of ammonia water in which 1.2 parts of ammonia was dissolved was added dropwise, the emulsion dispersion was heated to 40 ° C., and ethyl acetate was removed by vacuum distillation to prepare a colored resin emulsion. Next, glycerin 2 as a moisturizer was added to 66.7 parts of the above colored resin emulsion (solid content: 15% by weight).
0 part and 13.3 parts of water were added, and the mixture was stirred and mixed uniformly to prepare an inkjet printing ink (1). After filtering the colored resin emulsion with a filter having a pore size of 5 μm, the particle size of the colored resin particles was measured, and the average particle size was 170 nm.

Example 2 An organic solvent solution of a vinyl resin and an oil-soluble dye was prepared in the same manner as in Example 1, and then a pigment wet cake of anthraquinone red organic pigment (content of organic pigment: 2.5 wt. %, Average particle diameter 95 nm), 556 parts were added, and the viscosity was drastically lowered during the addition to cause phase conversion and an oil-in-water emulsion was obtained. To the above oil-in-water emulsion, 120 parts of ammonia water in which 1.2 parts of ammonia was dissolved in 122.7 parts of water was dropped, and after heating to 40 ° C., ethyl acetate was removed by vacuum distillation to obtain a colored resin emulsion. Was produced. In the obtained colored resin emulsion, the colored resin fine particles have a particle diameter of 18
Since it had two peaks at 5 nm and 860 nm,
When the particles with a large particle size were settled and removed by centrifugation, the peak at 860 nm disappeared and the average particle size was 38.
It was 0 nm. An inkjet printing ink (2) was prepared from the colored resin emulsion (average particle diameter of colored resin particles: 380 nm) after the centrifugation in the same manner as in Example 1.

(Example 3) In the same manner as in Example 1, after obtaining a water-in-oil emulsion from a vinyl resin, an organic solvent solution of an oil-soluble dye, and a pigment wet cake, instead of 586 parts of water, Ammonia water 706 in which ammonia 1.2 is dissolved
Parts were added. During the addition of this ammonia water, the viscosity drastically decreased and the water-in-oil type emulsion was phase-converted to obtain an oil-in-water type emulsion. Then, ethyl acetate was removed in the same manner as in Example 1 to prepare a colored resin emulsion. This colored resin emulsion is
Since the colored resin fine particles had two peaks at the particle diameters of 205 nm and 770 nm, when the large particles were sedimented and removed by centrifugation, the peak at 770 nm disappeared and the average particle diameter was 320 nm. Ink for inkjet printing (3) was prepared from the colored resin emulsion (average particle size of colored resin particles: 320 nm) after the centrifugation in the same manner as in Example 1.

COMPARATIVE EXAMPLE 1 The same vinyl-based resin and oil-soluble dye solution as in Example 1 were mixed with “CROMOPHT”.
13.9 parts of "AL Red 2B" (manufactured by Ciba Specialty Chemicals) and a pigment dispersant of styrene-maleic acid copolymer (trade name "DKS-DISCOAT N-1"
4 ", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and mixed with 7 parts by atomization by a salt milling method to obtain a pigment wet cake (average particle diameter of organic pigment: 88 nm, content: 15% by weight).
7 parts were gradually added to obtain a water-in-oil type emulsion.
Then, ethyl acetate was removed in the same manner as in Example 1,
A colored resin emulsion was prepared. In this colored resin emulsion, the average particle diameter of the colored resin fine particles was 185 nm. From this colored resin emulsion, an ink for inkjet printing (4) was prepared in the same manner as in Example 1.
Was prepared.

(Comparative Example 2) A pigment wet cake 5 similar to that of Example 1 was prepared after an organic solvent solution of vinyl resin was obtained in the same manner as in Example 1 except that an oil-soluble dye was not used.
49.3 parts by weight was added to obtain a water-in-oil emulsion. Subsequently, 546.3 parts by weight of water was added to invert the phase,
An oil-in-water emulsion was obtained. Next, 120 parts of ammonia water in which 1.2 parts of ammonia was dissolved was added, and ethyl acetate was removed in the same manner as in Example 1 to obtain a colored resin emulsion. In this colored resin emulsion, the average particle diameter of the colored resin fine particles was 237 nm. Further, an ink for inkjet printing (5) was prepared in the same manner as in Example 1.

The following evaluations were performed on the ink jet printing inks (1) to (5) obtained in the above Examples and Comparative Examples. (Evaluation of Inkjet Ejectability) One pixel is 100 μm × 300 using a piezo type inkjet printer.
The ink for inkjet printing was discharged onto a glass substrate divided into a size of μm to form a color filter. The ink for inkjet printing (1) has a color filter formed by landing on the target pixel.
No change in discharge accuracy was observed even if discharge was continued for 10 minutes or longer.

Ink for ink jet printing (2)
In (3) and (3), the color filter was formed by landing on the target pixel, but when the ejection was continued for 5 minutes, a deviation of the landing position was recognized, so the nozzle cleaning was performed. After the nozzle cleaning, the deviation of the landing position was eliminated. On the other hand, in the inkjet inks (4) and (5), the deviation of the landing position and the nozzles which were not ejected were observed from the initial stage of the ejection start, and the same phenomenon was observed even after the nozzle cleaning.

(Evaluation of Color Filter Coating Film) The color filter produced using the ink jet printing ink (1) was uniform and had a good surface smoothness. It was also confirmed that the hue was a coating film having a predetermined hue. The color filters produced by using the inkjet printing inks (2) and (3) were uniform and had a good surface smoothness. However, the hue was slightly more yellowish than the hue of the predetermined coating film. It is considered that this is because the red pigment settled down by the centrifugal sedimentation treatment. In the color filter produced by using the inkjet printing ink (4), most of the pixels were not formed accurately due to the deviation of the landing position, but when observed on some of the correctly formed pixels, it was partially found. A difference in film thickness was observed. It is considered that this is because the viscosity of the ink is high and it is difficult for the ink to spread uniformly. In the color filter produced by using the inkjet printing ink (5), most of the pixels were not accurately formed due to the deviation of the landing position, but when observing some of the correctly formed pixels, minute cracks were found. A clear coating film could not be obtained due to the inclusion of ". It is considered that this is because the coating film is difficult to be formed because the binder resin component is insufficient.

(Evaluation of Storage Stability of Ink) The obtained ink for ink jet printing was put in a glass container, and the container was allowed to stand for 1 week in a constant temperature bath at 40 ° C., and the change in the ink was visually observed. It was the street. Inkjet printing ink (1): No change in appearance was observed. Inkjet printing ink (2): No change in appearance was observed. Inkjet printing ink (3): No change in appearance was observed. Inkjet printing ink (4): The entire ink lost fluidity and gelled. Inkjet printing ink (5): A layer of sediment was observed at the bottom of the container.

[0099]

EFFECT OF THE INVENTION The colored resin emulsion of the present invention has the above-mentioned constitution and is excellent in ink jet discharge property and has good storage stability as an ink, and therefore, it is suitably used as an ink for ink jet printing for forming a color filter. You can

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/00 C08L 101/00 4J002 C08L 101/00 C09D 11/00 4J039 C09D 11/00 G02B 5/20 101 4J100 G02B 5/20 101 G02F 1/1335 505 G02F 1/1335 505 C08F 220: 06 // (C08F 220/58 220: 20 220: 06 B41J 3/04 101Y 220: 20) 101Z F term (reference) 2C056 FB01 FC02 2H048 BA47 BA57 BA64 BB02 BB42 2H086 BA53 BA55 BA59 BA60 BA62 2H091 FA04Y FB02 FB12 FC12 FD24 GA01 LA12 4F070 AA29 AA32 AA36 AA37 AA71 AA75 BF1 BG1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 041 BB1 041 EU006 FD096 GT00 HA07 4J039 AD12 BE01 BE02 BE22 GA24 4J100 AA02P AA03 P AA04P AB02P AB03P AC03P AC04P AC12P AD03R AE02P AE04P AE19R AG02P AG04P AJ01Q AJ02Q AJ08Q AJ09Q AL03P AL04P AL05P AL08P AL08R AL09R AL09P BA05P APRBA21P APRBA21R AM05P AM11P AM11P

Claims (12)

[Claims] 1. A colored resin emulsion in which fine colored resin fine particles having an average particle diameter of 50 to 500 nm made of a vinyl-based resin containing an organic pigment are dispersed in an aqueous medium, and the content of the organic pigment contained in the fine colored resin fine particles. Is vinyl resin 1
3 to 40 parts by weight with respect to 00 parts by weight, and the colored resin fine particles do not contain a pigment dispersant. 2. A colored resin emulsion in which colored resin fine particles having an average particle diameter of 50 to 500 nm, which are made of a vinyl resin containing an organic pigment and an oil-soluble dye, are dispersed in an aqueous medium, and are contained in the colored resin fine particles. A colored resin emulsion, wherein the total content of the pigment and the oil-soluble dye is 3 to 40 parts by weight with respect to 100 parts by weight of the vinyl resin, and the colored resin fine particles do not contain a pigment dispersant. 3. The vinyl resin comprises 100 parts by weight of a hydrophobic vinyl monomer and vinyl monomer 1 having an anionic group.
A copolymer obtained by copolymerizing a monomer mixture containing 30 to 30 parts by weight and 1 to 55 parts by weight of a vinyl monomer having a nonionic hydrophilic group. The colored resin emulsion described in 1. 4. The vinyl-based resin is a polymer obtained by polymerizing a monomer component containing a hydrophobic vinyl-based monomer, and is a polymerizable monomer represented by the following general formula (1). Is 10% by weight or more of the monomer component, The colored resin emulsion according to any one of claims 1 to 3, wherein ^{_{CH 2 = CR 1 CONHCH 2 OR}} 2 ···· (1) ( wherein, R ¹ represents a hydrogen or a methyl group, R ² represents an alkyl group having 3 to 6 carbon atoms) 5. A water-in-oil emulsion obtained by adding a pigment wet cake, which is an organic pigment containing water and not containing a pigment dispersant, to a solution prepared by dissolving a vinyl resin in an organic solvent, and uniformly mixing and dispersing the same. To obtain an oil-in-water emulsion by adding an aqueous medium containing no pigment to the obtained water-in-oil emulsion, and removing the organic solvent to remove it from the system. A method for producing a colored resin emulsion, which comprises a third step of removing the colored resin emulsion. 6. A water-in-oil emulsion obtained by adding a pigment wet cake, which is an organic pigment containing water and not containing a pigment dispersant, to a solution prepared by dissolving a vinyl resin in an organic solvent, and uniformly mixing and dispersing the pigment wet cake. In the first step, a water-in-oil type emulsion is added to the obtained water-in-oil type medium to convert it into an oil-in-water type emulsion, and a basic compound is added to the vinyl resin anion. A method for producing a colored resin emulsion, comprising a third step of ionizing a functional group and a fourth step of removing an organic solvent by distillation to remove it from the system. 7. The vinyl resin comprises 100 parts by weight of a hydrophobic vinyl monomer and a vinyl monomer 1 having an anionic group.
6. A copolymer obtained by copolymerizing a monomer mixture containing 30 to 30 parts by weight and 1 to 55 parts by weight of a vinyl monomer having a nonionic hydrophilic group.
Or the method for producing a colored resin emulsion according to item 6. 8. A vinyl-based resin is a polymer obtained by polymerizing a monomer component containing a hydrophobic vinyl-based monomer, and is a polymerizable monomer represented by the following general formula (1). Is 10% by weight or more of the monomer component, The method for producing a colored resin emulsion according to claim 5, wherein ^{_{CH 2 = CR 1 CONHCH 2 OR}} 2 ···· (1) ( wherein, R ¹ represents a hydrogen or a methyl group, R ² represents an alkyl group having 3 to 6 carbon atoms) 9. A vinyl resin 100 containing an organic pigment.
3 to 40 parts by weight with respect to parts by weight, the viscosity of the vinyl-based resin is 1000 mPa · s or less at 20 ° C., and the pigment wet cake contains 5 to 25% by weight of the organic pigment, and the average particle of the organic pigment. The diameter is 50 to 300 nm,
The method for producing a colored resin emulsion according to any one of claims 5 to 8, wherein the average particle diameter of the colored resin fine particles is 20 to 80%. 10. The method for producing a colored resin emulsion according to claim 5, wherein the oil-soluble dye is dissolved in the solution containing the vinyl resin. 11. The colored resin emulsion according to any one of claims 1 to 4 or any one of claims 5 to 10.
An ink for inkjet printing, comprising a colored resin emulsion produced by the method for producing a colored resin emulsion according to the item 1. and a humectant. 12. A color filter manufactured using the ink for inkjet printing according to claim 11.