JP2013205775A - Colored resin composition, color filter, liquid crystal display device, and organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored resin composition capable of achieving both of improvement in sensitivity and reduction in developing time for a coating film, which conventionally have a trade-off relationship, and to provide a color filter including a pixel formed using the colored resin composition, and a high quality liquid crystal display device and organic EL display device including the color filter.SOLUTION: A colored resin composition includes (A) dyestuff, (B) a solvent, (C) a binder resin, and (D) a polymerizable monomer. The polymerizable monomer includes a specific dendrimer.

Description

  The present invention relates to a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display device.

Conventionally, a photolithography method, a dyeing method, an electrodeposition method, and a printing method are known as methods for producing a color filter used in a liquid crystal display device or the like. Among these, from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, and the like, a photolithography method having excellent characteristics on average is most widely adopted.
In the photolithography method, a photosensitive resin layer containing a color material is formed on a substrate, and a process for obtaining a monochromatic pattern by patterning the layer is repeated three times to form R, G, and B color filter pixels. .

  The repetitive process for forming three color pixels of R, G, and B in the photolithography method is long and complicated as a whole, and the manufactured filter part often has a defect. For this reason, the correction process which detects a defective part and corrects a defective part as needed is performed. Examples of the defective portion include a development residue due to insufficient solubility in a developing solution, a white defect in which a part of a pixel is missing, a black defect due to a foreign matter, a water stain (white stain, development stain), and the like.

Further, from the viewpoint of productivity improvement and cost reduction, it has become mainstream to reduce the exposure amount, adjust the development time, and shorten the tact time. As a result, the above-mentioned defects are likely to occur. These have caused display defects and defects on the panel due to disconnection of the transparent electrode formed on the color filter, peeling of the pixels, and light leakage.
In order to solve this problem, for example, Patent Document 1 discloses the use of 2,2,2-trisacryloyloxymethylethylphthalic acid as the polymerizable compound.

JP 2007-148062 A

However, in the method described in Patent Document 1, although the problem of residue is improved, there may be a problem that the sensitivity of the coating film is lowered and the development time becomes long.
Further, due to a decrease in the sensitivity of the coating film, the curability of the pixels is lowered, and when the cross-sectional shape is observed, the edge linearity is inferior, and it may be difficult to obtain high-definition panel characteristics.
The sensitivity of the colored resin composition is that the film is more likely to be solidified, and there is usually a trade-off between this and shortening the development time, that is, improving the solubility in the developer. For this reason, it is extremely difficult to improve the sensitivity of the coating film and the development time at the same time.

When a dye is used for the color material, it is difficult to achieve both the linearity of the pixel edge and the development time, as compared with the case where a pigment is used for the color material, as estimated below.
When a dye is used, even when the photopolymerization initiator is exposed to light energy during exposure and becomes excited, the energy is transferred to the dye before the photopolymerization initiator generates radicals due to contact with the dye. Some of the photopolymerization initiators do not function to generate radicals.

  The above phenomenon occurs when a dye is used. The probability of contact with a photopolymerization initiator is greater in a dye that exists in a substantially monomolecular state than in a pigment that is associated in a colored resin composition. That is, when a dye is included rather than a pigment, there is a high probability that the energy of the photopolymerization initiator moves. Therefore, when the dye is included, the radical generation function of the photopolymerization initiator is not sufficient and the curability of the pixel tends to be insufficient as compared with the case of using a pigment.

In other words, when dyes are used, it is necessary to achieve both a reduction in development time that is in a trade-off relationship while the curability of the pixels tends to be insufficient. Is difficult.
That is, an object of the present invention is to provide a colored resin composition containing a dye and capable of achieving both a sensitivity of a coating film and a shortening of development time, both of which are conventionally in a trade-off relationship.

  Another object of the present invention is to provide a color filter having pixels formed using the colored resin composition, and a high-quality liquid crystal display device and organic EL display device having the color filter.

As a result of intensive studies, the present inventors have found that the above problem can be solved by containing a specific polymerizable monomer in the colored resin composition, and have reached the present invention.
That is, the gist of the present invention includes (A) a dye, (B) a solvent, (C) a binder resin and (D) a polymerizable monomer, and the (D) polymerizable monomer has the following formula ( 1)

(In the above formula (1), the arrow represents the binding site with the branched chain unit.)
The branched chain unit has the structure represented by the following formula (2)

(In the above formula (2), the arrow represents the side bonded to the core part or the branched chain unit, and n represents an integer.)
Having a structure represented by the following formula (3)

(In the above formula (3), R ¹ represents a hydrogen atom or a methyl group.)
The present invention resides in a colored resin composition, a color filter, a liquid crystal display device and an organic EL display device characterized by containing a dendrimer having a group represented by the formula (hereinafter sometimes referred to as “dendrimer of the present invention”).

The present invention can provide a colored resin composition that can achieve both trade-off sensitivity and shortening of development time, which are conventionally in a trade-off relationship.
In addition, the present invention can provide a color filter having pixels formed using the colored resin composition, and a liquid crystal display device and an organic EL display device having the color filter.

It is a section schematic diagram showing an example of an organic EL device which has a color filter of the present invention.

The constituent requirements and embodiments of the present invention will be described in detail below, but these are examples of the embodiments of the present invention, and the present invention is not limited to these contents.
“(Meth) acryl” and the like mean “at least one of acryl and methacryl” and “(meth) acrylate” and the like mean “at least one of acrylate and methacrylate”. “Meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”.

Further, “total solid content” means all components other than the solvent components described later, which are contained in the colored resin composition.
In the present invention, unless otherwise specified, the weight average molecular weight refers to a polystyrene-reduced weight average molecular weight (Mw) by GPC (gel permeation chromatography). “C.I.” means a color index (C.I.).

Furthermore, in the present invention, the “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the amount of base and the equivalent weight of KOH per 1 g of the solid content of the dispersant. is there. The measuring method will be described later. On the other hand, the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.
In the present invention, “aromatic ring” refers to both “aromatic hydrocarbon ring” and “aromatic heterocycle”.

The colored resin composition of the present invention contains (A) a dye, (B) solvent, (C) a binder resin and (D) a polymerizable monomer containing the dendrimer of the present invention, preferably (E) a photopolymerization initiating component. And / or a thermal polymerization initiating component and, if necessary, other components.
First, (D) the polymerizable monomer will be described in detail.
[(D) Polymerizable monomer]
The colored resin composition of the present invention comprises (D) a polymerizable monomer having the following formula (1) as a core part:

(In the above formula (1), the arrow represents the binding site with the branched chain unit.)
The branched chain unit has the structure represented by the following formula (2)

(In the above formula (2), the arrow represents the side bonded to the core part or the branched chain unit, and n represents an integer.)
Having a structure represented by the following formula (3)

(In the above formula (3), R ¹ represents a hydrogen atom or a methyl group.)
The dendrimer which has group represented by these is contained.
The dendrimer of the present invention is particularly preferably a compound represented by the following formula (4).

The dendrimer of the present invention can be obtained from, for example, Osaka Organic Chemical Industry Co., Ltd.
The molecular weight of the dendrimer of the present invention is usually 3,500 or less, preferably 3,000 or less, and usually 400 or more, preferably 500 or more.
Other polymerizable monomers may be contained in addition to the colored resin composition of the present invention and the dendrimer of the present invention.

The other polymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular compound, but it may be an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred).
The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation component described later when the colored resin composition of the present invention is irradiated with actinic rays. In addition, the (D) polymerizable monomer in this invention means the concept opposite to what is called a polymeric substance, and also includes a dimer, a trimer, and an oligomer other than a monomer in a narrow sense.

  (D) Examples of the ethylenic compound in the polymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and unsaturated carboxylic acids; Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Esterification of unsaturated carboxylic acids with polyvalent carboxylic acids and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds described above An ester obtained by the reaction; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound;

Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. In addition, the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid portion, a crotonic acid portion replaced with a crotonic acid portion, or a maleic acid ester replaced with a maleic acid portion, etc. Is mentioned.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound may be a single substance or a mixture. Representative examples are condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol A condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane A reaction product with a group-containing hydroxy compound is exemplified.

In addition, examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .
Among these, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, pentaerythritol or (meth) acrylic acid esters of dipentaerythritol are more preferred, and dipentaerythritol hexa (meth) acrylate is particularly preferred.

  The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having a group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

These monomers may be used alone, but since it is difficult to obtain a single compound in production, a mixture of two or more kinds may be used.
Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as (D) polymeric monomer as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g.

When it is within the above range, the development and dissolution characteristics are hardly deteriorated, and the production and handling are easy. Furthermore, it is preferable because the photopolymerization performance is hardly lowered and the curability such as the surface smoothness of the pixel is good.
In the present invention, a more preferred polyfunctional monomer having an acid group is, for example, a mixture containing succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate as a main component. It is also possible to use this polyfunctional monomer in combination with another polyfunctional monomer.

In the colored resin composition of the present invention, the content of the polymerizable monomer (D) is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, based on the total solid content. Usually, it is 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less.
In addition, the content of the dendrimer of the present invention in the polymerizable monomer (D) is usually 5% by weight or more, preferably 10% by weight or more, and usually 100% by weight or less in the total solid content.
Within the above range, it is preferable in that the effect of the present invention can be obtained satisfactorily.

[(A) Dye]
In the present invention, the dye (A) that can be used as a colorant is not particularly limited as long as the effects of the present invention are not impaired. For example, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes Dyes, nitro dyes, carbonyl dyes, methine dyes, cyanine dyes, triarylmethane dyes and the like are preferred.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

Examples of the triarylmethane dye include those described in International Publication No. 2009/107734 pamphlet.
Furthermore, examples of the cyanine dye include those described in Japanese Patent Application No. 2010-142748, and preferred embodiments thereof are also the same.
The (A) dye in the present invention may be composed of only the above-mentioned dye, but other colorants can be used in combination with the dye. As other coloring materials, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like.
As the pigment in the present invention, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition, as its structure, azo, phthalocyanine, quinacridone, benzimidazolone,
In addition to organic pigments such as isoindoline, quinophthalone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used.

As these usable pigments, for example, pigments described in JP-A-2009-025813 can be used.
The content ratio of all the color materials in the colored resin composition of the present invention, that is, the total content ratio of the (A) dye and other color materials is usually 1 to 50% by weight with respect to the total solid content. , Preferably 3 to 40% by weight, more preferably 5 to 30% by weight.
When it is within the above range, the film thickness is appropriate with respect to the color density, and it is easy to control the gap when forming a liquid crystal cell. Furthermore, the dispersion stability is high, and it is difficult to place reaggregation or thickening.

[(B) Solvent]
The solvent (B) contained in the colored resin composition of the present invention has a function of adjusting the viscosity by dissolving or dispersing each component contained in the colored resin composition.
The solvent (B) may be any solvent as long as it can dissolve or disperse each component constituting the colored resin composition, and a solvent having a boiling point in the range of 100 to 200 ° C. is preferably selected. More preferably, it has a boiling point of 120-170 ° C.
Examples of such solvents include the following.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene Glycol monoalkyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol monomethyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycol alkyl ether acetates such as ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;
Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;

Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;

Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:
These solvents may be used alone or in combination of two or more.

Of these solvents, glycol monoalkyl ethers are preferred from the viewpoint of the solubility of the dye (A) in the present invention. Among these, propylene glycol monomethyl ether is particularly preferable from the viewpoint of solubility of various components in the colored resin composition.
In addition, for example, in the case of containing a pigment (F) described later as an optional component, the balance of coatability, surface tension, etc. is good, and from the viewpoint that the solubility of the constituent components in the colored resin composition is relatively high, It is more preferable to use a mixture of glycol alkyl ether acetates. In addition, in colored resin compositions containing pigments, glycol monoalkyl ethers are highly polar and tend to aggregate the pigment, which may reduce storage stability, such as increasing the viscosity of the colored resin composition. For this reason, it is preferable that the amount of the glycol monoalkyl ether used is not excessively large, and the proportion of the glycol monoalkyl ether in the solvent (B) is preferably 5 to 50% by weight, more preferably 5 to 30% by weight. .

Further, from the viewpoint of suitability for a slit coat method corresponding to a recent large substrate or the like, it is also preferable to use a solvent having a boiling point of 150 ° C. or higher. In this case, the content of such a high boiling point solvent is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably 5 to 30% by weight based on the total amount of the solvent (B). If the amount of the high boiling point solvent is too small, for example, a dye component may precipitate and solidify at the tip of the slit nozzle to cause foreign matter defects, and if it is too large, the drying speed of the composition will be slowed down. There is a concern that the filter manufacturing process may cause problems such as tact defects in the vacuum drying process and pin marks of prebaking.
The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be included separately. .

The colored resin composition of the present invention may be used for color filter production by the ink jet method, but in color filter production by the ink jet method, the ink emitted from the nozzle is very small, from several to several tens pL, There is a tendency for the solvent to evaporate and the ink to concentrate and dry before landing on the periphery of the nozzle opening or in the pixel bank. In order to avoid this, it is preferable that the solvent has a high boiling point. Specifically, it is preferable that the solvent (B) contains a solvent having a boiling point of 180 ° C. or higher. In particular, it is preferable to contain a solvent having a boiling point of 200 ° C. or higher, particularly 220 ° C. or higher. Moreover, it is preferable that the high boiling point solvent whose boiling point is 180 degreeC or more is 50 weight% or more in (B) solvent. When the ratio of such a high boiling point solvent is less than 50% by weight, the effect of preventing evaporation of the solvent from the ink droplets may not be sufficiently exhibited.

  In the colored resin composition of the present invention, the content of the (B) solvent is not particularly limited, but the upper limit is usually 99% by weight. When the content of the (B) solvent in the composition exceeds 99% by weight, the concentration of each component excluding the (B) solvent may become too small to form a coating film. On the other hand, the lower limit of the content of the solvent (B) is usually 75% by weight, preferably 80% by weight, and more preferably 82% by weight in consideration of viscosity suitable for coating.

[(C) Binder resin]
(C) What preferable binder resin changes with the hardening means of a colored resin composition.
When the colored resin composition of the present invention is a photopolymerizable resin composition, examples of the (C) binder resin include JP-A-7-2072111, JP-A-8-259876, and JP-A-10-300922. The polymer compounds described in JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, and the like can be used. However, among them, the following resins (C-1) to (C-5) are preferable.

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Resin to be added, or an alkali-soluble resin (hereinafter referred to as “resin (C-1)”) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. .)
(C-2): Carboxyl group-containing linear alkali-soluble resin (C-2) (hereinafter sometimes referred to as “resin (C-2)”)
(C-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter sometimes referred to as “resin (C-3)”).
(C-4): (Meth) acrylic resin (hereinafter sometimes referred to as “resin (C-4)”)
(C-5): Epoxy acrylate resin having a carboxyl group (hereinafter sometimes referred to as “resin (C-5)”)
Of these, the resin (C-1) is particularly preferable, and the resin will be described below.
The resins (C-2) to (C-5) may be anything as long as they are dissolved in an alkaline developer and are soluble to the extent that the desired development processing is performed. It is the same as that described as the same item of 2009-025813 gazette. The preferred embodiment is also the same.

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. As one of particularly preferable resins of the alkali-soluble resin resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction, or an epoxy group, Unsaturated in 10 to 100 mol% of the epoxy group of the copolymer with respect to the copolymer of 5 to 90 mol% of (meth) acrylate and 10 to 95 mol% of other radical polymerizable monomer Examples thereof include a resin obtained by adding a monobasic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of a hydroxyl group generated by the addition reaction.

Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

  The other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is not particularly limited as long as the effects of the present invention are not impaired. For example, vinyl aromatics, dienes, (meth) Examples include acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, and the like, and in particular, mono (meth) having a structure represented by the following formula (7) Acrylate is preferred.

  The repeating unit derived from the mono (meth) acrylate having the structure represented by the following formula (7) contains 5 to 90 mol% among the repeating units derived from “other radical polymerizable monomers”. The content is preferably 10 to 70 mol%, more preferably 15 to 50 mol%.

In the above formula (7), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the following formula (8).

The formula ^{(8), R} 91 ~R ⁹⁸ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ may be connected to each other to form a ring.
The ring formed by connecting R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
Among these, among the structures represented by the formula (8), those represented by the following structural formulas (8a), (8b), or (8c) are particularly preferable.

In addition, the mono (meth) acrylate which has a structure represented by the said Formula (8) may be used individually by 1 type, and may use 2 or more types together.
As "other radical polymerizable monomers" other than the mono (meth) acrylate having the structure represented by the formula (8), the heat resistance and strength excellent in the colored resin composition can be improved. , Styrene, (n-butyl) (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate , (Meth) acrylic acid-2-hydroxyethyl, N-phenylmaleimide, N-cyclohexylmaleimide.

The content of the repeating unit derived from at least one selected from the above monomer group is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.
A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer.
In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Is preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter. What consists of 70 mol% and the latter 70-30 mol% is especially preferable.

Within the above range, heat resistance and film strength are sufficient, which is preferable.
The epoxy group portion of the epoxy group-containing copolymer synthesized as described above is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).
Here, as an unsaturated monobasic acid added to an epoxy group, a well-known thing can be used, For example, unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned.

Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These may be used alone or in combination of two or more.

By adding such components, polymerizability can be imparted to the binder resin used in the present invention.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. It is preferable for it to be in the above range since the colored resin composition is excellent in stability over time. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a copolymer.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferred. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

By adding such a component, alkali solubility can be imparted to the binder resin used in the present invention.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%.

Within the above range, the remaining film ratio and solubility during development are sufficient, which is preferable.
In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.
Furthermore, in order to improve photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be. Such a resin structure is described in, for example, Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.

The polystyrene-reduced weight average molecular weight (Mw) of the above-described binder resin (C-1) measured by GPC (gel permeation chromatography) is preferably 3000 to 100,000, and particularly preferably 5000 to 50000. Within the above range, heat resistance, film strength, and solubility in a developer are preferable.
Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

In addition, the acid value of binder resin (C-1) is 10-200 mg-KOH / g normally, Preferably it is 15-150 mg-KOH / g, More preferably, it is 25-100 mg-KOH / g. If the acid value is too low, the solubility in the developer may be reduced. Conversely, if it is too high, film roughening may occur.
Content of (C) binder resin in a colored resin composition is 0.1 to 80 weight% normally in a total solid, Preferably it is 1 to 60 weight%.

Within the above range, the adhesion to the substrate is good, the permeability of the developer to the exposed area is moderate, and the surface smoothness and sensitivity of the pixels are good.
In the colored resin composition of the present invention, the P / M ratio (P represents the content of the binder resin (C) in the colored resin composition, and M represents the (D) polymerizable monomer in the colored resin composition. Is usually 0.5 or more, preferably 1 or more, more preferably 2 or more, and usually 5 or less, preferably 4.5 or less, more preferably 4 or less.
It is preferable in the said range at the point from which the hardening of this invention is acquired favorably.

[(E) Photopolymerization initiation component and / or thermal polymerization initiation component]
The colored resin composition of the present invention preferably contains (E) a photopolymerization initiation component and / or a thermal polymerization initiation component for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.
In particular, when the colored resin composition of the present invention includes a resin having an ethylenic double bond as the component (C), or includes an ethylenic compound as the component (D), it directly absorbs light, or It is preferable to contain a photopolymerization initiating component that has a function of generating a polymerization active radical and / or a thermal polymerization initiating component that generates a polymerization active radical by heat. In the present invention, the component (E) as a photopolymerization initiation component refers to a photopolymerization initiator (hereinafter also referred to as “(E1) component”), a polymerization accelerator (hereinafter, optionally referred to as “(E2) component”). ")" And a sensitizing dye (hereinafter also referred to as "(E3) component").

[(E) Photopolymerization initiation component]
The (E) photopolymerization initiating component in the present invention is usually a mixture of (E1) a photopolymerization initiator and, if necessary, (E2) a polymerization accelerator and (E3) an additive such as a sensitizing dye. And is a component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of (E1) photopolymerization initiator constituting the photopolymerization initiating component include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197, etc .; JP-A-10-300922 Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl-s -Radical activators such as triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives And oxime ester derivatives described in JP-A No. 2000-80068 and the like.

Specific examples include photopolymerization initiators described in International Publication No. 2009/107734 pamphlet and the like.
Among these photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.

  The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), and a compound represented by the following formula (XI).

(In formula (XI), R ¹⁰¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroaryl group having 4 to 25 carbon atoms. An alkyl group, each of which may have a substituent, or R ¹⁰¹ may be bonded to X or Z to form a ring;
R ¹⁰² represents an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 10 carbon atoms. , An aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroaryloyl group having 3 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms, It may have a substituent.
X represents a divalent aromatic hydrocarbon ring group and / or an aromatic hetero group formed by condensation of two or more rings which may have a substituent.

Z represents an aromatic ring group which may have a substituent. )
Of the compounds represented by the formula (XI), compounds in which X is a carbazole ring which may have a substituent are preferable. Specifically, compounds represented by the following formula (XII) Among them, the compound represented by the following formula (XIII) is particularly preferable.

(Wherein R ¹⁰¹ , R ¹⁰² and Z have the same meanings as in formula (XI), R ^103.
To R ¹⁰⁹ is a hydrogen atom or an arbitrary substituent independently. )

(In the formula, R ^101a represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following formula (XIIIa).

(Wherein R ¹⁰³ and R ¹⁰⁴ each independently represent a hydrogen atom, a phenyl group or an N-acetyl-N-acetoxyamino group.
* Represents a binding site. )
R ^102a represents an alkanoyl group having 2 to 4 carbon atoms, and X ^a represents a 3,6-carbazolyl group in which the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms. Za represents ^a phenyl group which may be substituted with an alkyl group or a naphthyl group which may be substituted with a morpholino group. )
In addition, benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2,4-diethylthioxanthone, etc. Examples also include thioxanthone derivatives, benzoate derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like.

Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable. In particular, oxime ester derivatives are preferable.
Examples of the (E2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Examples thereof include mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.
Each of these (E1) photopolymerization initiator and (E2) polymerization accelerator may be used alone or in combination of two or more.

  Further, (E3) sensitizing dye is used for the purpose of increasing the sensitivity as required. As the sensitizing dye, an appropriate one is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; No. 239703, JP-A-5-289335, etc. Coumarin dyes having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes; Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681 JP, 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP 5-10. 761 No., JP-A-5-210240, dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

(E3) A sensitizing dye may also be used alone or in combination of two or more.
In the colored resin composition of the present invention, the content of these (E) photopolymerization initiating components is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.8% by weight in the total solid content. It is 5% by weight or more, usually 40% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight or less.
Within the above range, the sensitivity to the exposure light beam is good, the solubility of the unexposed part in the development station is good, and it is preferable in that it is difficult to induce poor development.

[(E) Thermal polymerization starting component]
Specific examples of the (E) thermal polymerization initiating component that may be contained in the colored resin composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used. More specifically, for example, a thermal polymerization initiating component described in International Publication No. 2009/107734 can be used.
These thermal polymerization initiating components may be used alone or in combination of two or more.

[Other optional ingredients]
In addition to the above components, the colored resin composition of the present invention comprises a surfactant, an organic carboxylic acid and / or an organic carboxylic acid anhydride, a thermosetting compound, a plasticizer, a thermal polymerization inhibitor, a storage stabilizer, a surface It may contain a protective agent, an adhesion improver, a development improver, and the like. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used.
Moreover, when it contains the below-mentioned (F) pigment, you may contain a dispersing agent and a dispersing aid.

[(F) Pigment]
The colored resin composition of the present invention may contain (F) a pigment within a range not impairing the effects of the present invention for the purpose of improving the heat resistance of the obtained color filter.
(F) As a pigment, for example, when forming a pixel of a color filter, pigments of various colors such as blue and purple can be used. Examples of the chemical structure include organic pigments such as phthalocyanine, quinacridone, benzimidazolone, dioxazine, indanthrene, and perylene. In addition, various inorganic pigments can be used. Hereinafter, specific examples of usable pigments are indicated by pigment numbers.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like.

Among these, a blue copper phthalocyanine pigment is preferable, and examples of the copper phthalocyanine pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and the like are preferable, and C.I. I. Pigment Blue 15: 6.
For this reason, when the colored resin composition of this invention contains a blue pigment, it is 80 weight% or more with respect to the total content of a blue pigment, Especially 90 weight% or more, Especially 95-100 weight% is C.I. I. Pigment Blue 15: 6 is preferable.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like.
Among these, a purple dioxazine pigment is preferable, and as the dioxazine pigment, C.I. I. Pigment Violet 19 and 23 are preferable, and C.I. I. Pigment Violet 23.

For this reason, when the colored resin composition of this invention contains a purple pigment, it is 80 weight% or more with respect to the total content of a purple pigment, Especially 90 weight% or more, Especially 95-100 weight% is C.I. I. Pigment Violet 23 is preferable.
These may be used alone or in a combination of two or more in any combination and ratio.

The (F) pigment used in the colored resin composition of the present invention preferably has a small average primary particle diameter from the viewpoint of forming a high-contrast pixel. Specifically, the average primary particle diameter is 40 nm or less. Is preferable, and it is more preferable that it is 35 nm or less.
Particularly for the blue copper phthalocyanine pigment, the average primary particle size is preferably 40 nm or less, more preferably 35 nm or less, and still more preferably 20 to 30 nm.

Moreover, about a dioxazine pigment, an average primary particle diameter becomes like this. Preferably it is 40 nm or less, More preferably, it is 25-35 nm. From the viewpoint that the pigment is less likely to aggregate in the colored resin composition, it is preferable that the average primary particle size is not too small.
Here, the average primary particle size of the (F) pigment is a value measured and calculated by the following method.

First, (F) a pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). From this image, the particle size of each pigment particle is determined for a plurality of (usually about 200 to 300) pigment particles, with the diameter corresponding to the area circle converted to the diameter of a circle having the same area.
Using the obtained primary particle size value, the number average value is calculated according to the following formula to obtain the average particle size.
The particle diameter of each pigment _{particle: X 1, X 2, X} 3, X 4, ····, X i, ······ X m

{Blending amount}
In the present invention, when the pigment (F) is contained, the content of the pigment in the colored resin composition is usually 80% by weight or less, preferably 50% by weight or less in the total solid content.
Moreover, content with respect to 100 weight part of said (A) dye is 2000 weight part or less normally, Preferably it is 1000 weight part or less.
By setting it within the above-mentioned range, it is preferable because the heat resistance of the obtained pixel is likely to be better without greatly affecting the transmittance of the dye.

[Dispersant]
When the colored resin composition of the present invention contains (F) a pigment, it is preferable to further contain a dispersant.
The dispersant in the present invention is not particularly limited as long as the pigment is dispersed and can maintain stability.
For example, cationic, anionic, nonionic or amphoteric dispersants can be used, but polymer dispersants are preferred. Specific examples include block copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate esters of polymer copolymers, and cationic comb graft polymers. Of these dispersants, block copolymers, polyurethanes, and cationic comb graft polymers are preferred. In particular, a block copolymer is preferable, and among these, a block copolymer composed of an A block having solvophilicity and a B block having a functional group containing a nitrogen atom is preferable.

Specifically, the B block having a nitrogen atom-containing functional group includes a unit structure having a quaternary ammonium base and / or an amino group in the side chain, while the solvophilic A block includes a quaternary ammonium. Examples include a unit structure having no base and amino group.
The B block constituting the acrylic block copolymer has a unit structure having a quaternary ammonium base and / or an amino group, and has a pigment adsorption function.

Further, when the B block has a quaternary ammonium base, the quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group. Good.
Examples of such block copolymers include those described in JP-A-2009-025813.

Moreover, the colored resin composition of the present invention may contain a dispersant other than those described above. Examples of other dispersants include those described in JP-A-2006-343648, for example.
When the colored resin composition of the present invention contains (F) a pigment, the content of the dispersant in the total solid content is 2 to 1000% by weight, particularly 5 to 500% by weight of the total content of (F) pigment. %, Particularly 10 to 250% by weight.
By setting it within the above range, it is preferable in that good pigment dispersibility can be ensured without affecting the heat resistance of the dye, and the pigment dispersion stability becomes better.

[Dispersion aid]
The colored resin composition of the present invention may contain a dispersion aid. The dispersion aid here may be a pigment derivative. Examples of the pigment derivative include JP-A Nos. 2001-220520, 2001-271004, 2002-179976, and 2007-. Various compounds described in Japanese Patent Application Publication No. 113000 and Japanese Patent Application Publication No. 2007-186681 can be used.

  The content of the dispersion aid in the colored resin composition of the present invention is usually 0.1% by weight or more, usually 30% by weight or less, preferably 20% by weight or less, based on the total solid content of the pigment. Preferably it is 10 weight% or less, More preferably, it is 5 weight% or less. By controlling the addition amount within the above range, it is preferable in that the effect as a dispersion aid is exhibited and the dispersibility and dispersion stability are better.

[Dispersion resin]
The colored resin composition of the present invention may contain a part or all of the resin selected from the (C) binder resin or other binder resins as the following dispersion resin.
Specifically, in [Preparation Method of Colored Resin Composition], which will be described later, by adding (C) binder resin together with the components such as the above-mentioned dispersant, the (C) binder resin is combined with the dispersant. It contributes to the dispersion stability of the pigment (F) by a synergistic effect. As a result, the amount of dispersant added may be reduced, which is preferable. Further, it is preferable because the developability is improved, the undissolved matter does not remain in the non-pixel portion of the substrate, and the adhesion of the pixel to the substrate is improved.
Thus, the (C) binder resin used in the dispersion treatment step may be referred to as a dispersion resin. The dispersion resin is preferably used in an amount of about 0 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of the pigment in the colored resin composition.

[Preparation Method of Colored Resin Composition]
In the present invention, the colored resin composition can be prepared by an appropriate method. For example, the (A) dye, the (C) binder resin, and the dendrimer of the present invention are used as the solvent (B) and as necessary. It can be prepared by mixing with optional ingredients.
In addition, as a preparation method in the case of containing (F) a pigment, in the solvent containing (F) pigment, in the presence of a dispersing agent and a dispersing aid to be added if necessary, (C) a binder resin may be used. A pigment dispersion liquid is prepared by mixing and dispersing together with the parts, for example, using a paint shaker, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, and the like. In the pigment dispersion, (A) a dye, (C) a binder resin and the dendrimer of the present invention, if necessary (D) a polymerizable monomer other than the dendrimer of the present invention, (E) a photopolymerization initiating component and / or The method of preparing by adding a thermal polymerization initiating component, etc., and mixing can be mentioned.

[Application of colored resin composition]
The colored resin composition of the present invention is usually in a state where all the constituent components are dissolved or dispersed in a solvent. Such a colored resin composition is supplied onto a substrate to form components such as a color filter, a liquid crystal display device, and an organic EL display device.
Hereinafter, as an application example of the colored resin composition of the present invention, an application as a pixel of a color filter, a liquid crystal display device (panel) and an organic EL display device using them will be described.

<Color filter>
The color filter of the present invention has a pixel formed from the colored resin composition of the present invention.
The method for forming the color filter of the present invention will be described below.
The pixel of the color filter can be formed by various methods. Here, although the case where it forms by the photolithographic method using a photopolymerizable colored resin composition is demonstrated to an example, a manufacturing method is not limited to this.

  First, on the surface of the substrate, if necessary, a black matrix is formed so as to partition a portion for forming pixels, and after applying the colored resin composition of the present invention on this substrate, pre-baking is performed. The solvent is evaporated to form a coating film. Then, after exposing this coating film through a photomask, developing with an alkali developer, dissolving and removing the unexposed portion of the coating film, and then post-baking, each of red, green, and blue A color filter can be manufactured by forming a pixel pattern.

The substrate used for forming the pixels is not particularly limited as long as it is transparent and has an appropriate strength. For example, polyester resin, polyolefin resin, polycarbonate resin, acrylic resin, thermoplastic resin Examples thereof include a sheet made, an epoxy resin, a thermosetting resin, and various glasses.
In addition, these substrates may be appropriately subjected to pretreatment as desired, such as thin film formation treatment with a silane coupling agent or urethane resin, surface treatment such as corona discharge treatment or ozone treatment, if desired.

When applying the colored resin composition to the substrate, a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, a spray coating method, and the like can be given. Of these, the slit and spin method and the die coating method are preferable.
The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, particularly preferably 0.8 to 5.0 μm as the film thickness after drying.

Within the above range, it is easy to adjust the gap in the pattern development and liquid crystal cell forming process,
Moreover, it is preferable at the point which a desired color expression is easy.
As the radiation used in the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.

  The light source used for image exposure for using radiation having a wavelength of 190 to 450 nm is not particularly limited. Lamp light sources such as medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, and the like. An optical filter can also be used when used by irradiating light of a specific wavelength.

Exposure of radiation, 10~10,000J / ^{m 2} is preferred.
Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-di- or tri-ethanolamine, mono-di-, or tri -Methylamine, mono-, di-, or tri-ethylamine, mono-, or di-isopropylamine, n-butylamine, mono-, di-, or tri-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium Hydroxide (TMAH) Aqueous solution of an organic alkaline compound choline are preferred.

An appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or the like can be added to the alkali developer. In addition, it is usually washed with water after alkali development.
As the development processing method, any method such as an immersion development method, a spray development method, a brush development method, and an ultrasonic development method can be used. The development conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, more preferably 40 ° C. or lower. Is preferred.
The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

  When the color filter thus produced is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is and used as a part of a component such as a color display or a liquid crystal display device. Although used, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed. In the vertical alignment type driving method (MVA mode), ribs may be formed. Further, a column structure (photo spacer) by a photolithography method may be formed instead of the bead dispersion type spacer.

<Liquid crystal display device>
The liquid crystal display device of the present invention uses the above-described color filter of the present invention. There is no restriction | limiting in particular about the model and structure of the liquid crystal display device of this invention, It can assemble in accordance with a conventional method using the color filter of this invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun, September 29, 1989, Japan Society for the Promotion of Science 142nd Committee).

<Organic EL display device>
When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, on a blue color filter in which pixels 20 are formed on a transparent support substrate 10 by the colored resin composition of the present invention. A multicolor organic EL element is manufactured by laminating the organic light-emitting body 500 through the organic protective layer 30 and the inorganic oxide film 40.

  As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In the following examples, “part” represents “part by weight”.

(Reference Synthesis Example 1: Synthesis of Resin A)
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. 20 parts by weight of styrene, 57 parts by weight of glycidyl methacrylate and 82 parts by weight of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto, and the mixture was further stirred at 120 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 parts by weight of trisdimethylaminomethylphenol and 0.12 parts by weight of hydroquinone were added to 27 parts by weight of acrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Then, 52 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 120 ° C. for 3.5 hours. The weight average molecular weight Mw measured by GPC of the resin A thus obtained was about 15000. The structure of Resin A was as shown below (polymer compound containing the following four types of repeating units).

(Reference Synthesis Example 2: Synthesis of Resin B)
114.0 g of propylene glycol monomethyl ether acetate was placed in a 500 ml four-necked flask and heated to 85 ° C. while performing nitrogen bubbling. To this was added 100.1 g (0.55 mol) of cyclohexyl methacrylate, 33.3 g (0.45 also) of methacrylic acid, and 4.925 g (0.03 mol) of 2.2′-azobis (isobutyronitrile) in propylene glycol. It melt | dissolved in 96.45g of monomethyl ether acetate, and was dripped over 4 hours. After the dropwise addition, the reaction solution was further stirred for 2 hours while maintaining the temperature at 85 ° C., and thereafter the nitrogen bubbling was stopped and the temperature was raised to 100 ° C. for 1 hour. The weight average molecular weight Mw measured by GPC of the resin B thus obtained was about 15000, and the acid value was 190 mgKOH / g.

  (Reference Synthesis Example 3: Synthesis of Dye A)

  Reaction 1: A solution of compound 17 (10 g) in N, N-dimethylformamide (100 ml) was cooled in an ice bath, sodium hydride (60%, 4.3 g) was added, and after stirring for a while, compound 18 (6.5 g) ) Was added in small portions. After stirring at room temperature for 5 hours, water was added, extracted with dichloromethane, and purified by silica gel column chromatography to obtain compound 3 (3.1 g).

  Reaction 2: Phosphorus oxychloride (1.8 ml) was added to a mixture of compound 3 (5.61 g), compound 4 (2.65 g) and toluene (15 ml), and the mixture was stirred at 115 ° C. for 2 hours. After returning to room temperature, saturated brine (30 ml) was added, and the mixture was extracted twice with chloroform. The product was purified by silica gel column chromatography (silica gel 300 g, chloroform / methanol 1 / 0-10 / 1/7/1), and the resulting solid was washed with hexane to obtain compound 5 (9.23 g).

Reaction 3: A mixture of compound 5 (11.40 g), compound 6 (4.88 g) and methanol (146 ml) was stirred at 50 ° C. for 1 hour, added to water, and the solid was collected by filtration. The solid was washed with methanol / water: 2/1 (220 ml) and again washed with methanol / water: 2/1 (72 ml) to give Dye A (13.9 g).
[Preparation of blue pigment dispersion]
C. I. Pigment Blue 15: 6 is 12.0 parts by weight, the dispersant is BYK-LPN21116 (manufactured by Big Chemie) at 6.0 parts by weight in terms of dispersant solids, and the resin B prepared in Reference Synthesis Example 2 is in terms of solids 4.0 parts by weight and 78.0 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed and stirred with a stirrer for 3 hours to prepare a mill base having a solid content concentration of 20% by weight. This mill base was subjected to a dispersion treatment using 600 parts by weight of 0.5 mmφ zirconia beads in a bead mill apparatus at a peripheral speed of 10 m / s and a residence time of 3 hours to obtain a blue pigment dispersion (1).

[Preparation of colored resin composition]
The resin A synthesized in Reference Synthesis Example 1 and the dye A synthesized in Reference Synthesis Example 3 were mixed with other components so as to have the composition described in Table 1 to prepare a colored resin composition.
Table 2 shows the types of the (D) polysynthetic monomers used in each Example 1 and Comparative Examples 1 to 3.

In addition, all the numerical values in Table 1 represent parts by weight of each component to be added.
In mixing, the components were stirred for 1 hour or more until they were sufficiently mixed, and finally filtered through a 5 μm piece filter to remove foreign matters.

Moreover, each compound in Table 1 is as follows.
PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

The structural formula of V # 1000 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) shown in Table 2 is a compound represented by the formula (4).
[Evaluation method]
[1] Measurement of dissolution time and measurement of line width of photocured portion On the glass substrate AN100 (manufactured by Asahi Glass Co., Ltd.) which has been washed and cut into 5 cm square, each of the above colored resin compositions is dried by a spin coating method. It apply | coated so that it might become 2 micrometers, and dried under reduced pressure. When spray development was performed at a developer temperature of 26 ° C. and a pressure of 0.25 MPa using a 0.04 wt% aqueous potassium hydroxide solution, the time during which the colored resin composition in the unexposed area was completely dissolved and the glass substrate was exposed was measured. The dissolution time (BT: seconds) of the colored resin composition was used.

[2] Evaluation of linearity On the glass substrate AN100 (Asahi Glass Co., Ltd.) cut to 5 cm square after being washed, each of the colored resin compositions is applied by spin coating so as to have a dry film thickness of 3.2 μm. Dried.
Thereafter, using a photomask having a linear pattern with a width of 50 μm and a length of 30 mm, the entire surface was exposed at an exposure amount of 40 mJ / cm ² , and a developer temperature of 26 ° C. using a 0.04 wt% potassium hydroxide aqueous solution. And spray development at a pressure of 0.25 MPa. The development time was set to dissolution time + 20 seconds. After development, the substrate was washed with sufficient pure water, dried with clean air, and baked in a 230 ° C. oven for 20 minutes. Thereafter, the linearity of the pattern was evaluated with a 50 × optical microscope.

In addition, the thing with favorable linearity was set as (circle), the thing with a fine crack in a pattern (triangle | delta), and the thing with many fine cracks was set as x.
The results are summarized in Table 3.

As shown in Table 3, Example 1 has a shorter dissolution time in the developer than any of Comparative Examples 1 to 3. In addition, Example 1 has better linearity than any of Comparative Examples 1 to 3. That is, the colored resin composition of the present invention achieves both a shortening of the dissolution time in the developer and an improvement in sensitivity, both of which are conventionally traded off.
For this reason, the deterioration of the manufacturing yield due to the long dissolution time in the developer is suppressed, and the sensitivity is further improved.
Furthermore, the color filter which has the pixel formed using the colored resin composition of this invention, and the liquid crystal display device and organic electroluminescent display device which have this color filter are high quality.

DESCRIPTION OF SYMBOLS 100 Organic EL element 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 500 Organic light-emitting body 51 Hole injection layer 54 Electron injection layer

Claims (7)

(A) a dye, (B) a solvent, (C) a binder resin and (D) a polymerizable monomer,
The (D) polymerizable monomer has the following formula (1) as a core part:

(In the above formula (1), the arrow represents the binding site with the branched chain unit.)
The branched chain unit has the structure represented by the following formula (2)

(In the above formula (2), the arrow represents the side bonded to the core or branched chain unit, and n represents an integer.)
Having a structure represented by the following formula (3)

(In the above formula (3), R ¹ represents a hydrogen atom or a methyl group.)
A colored resin composition comprising a dendrimer having a group represented by the formula:   (D) The colored resin composition according to claim 1, wherein the dendrimer in the polymerizable monomer is contained in an amount of 5% by weight or more and 10% by weight or less based on the total solid content. A colored resin composition, wherein P / M in the colored resin composition is 0.5 or more and 5 or less.
(P represents the content of (C) binder resin in the colored resin composition, and M represents the content of (D) polymerizable monomer in the colored resin composition.)   The colored resin composition according to claim 1, further comprising (E) a photopolymerization initiation component and / or a thermal polymerization initiation component.   A color filter comprising a pixel formed using the colored resin composition according to claim 1.   A liquid crystal display device comprising the color filter according to claim 5.   An organic EL display device comprising the color filter according to claim 5.

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