JP2005202134A - Photosensitive resin composition for color filter and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for a color filter having such high photocurability that it is thoroughly cured with small light exposure in curing, and improved in accuracy of a pattern shape after development because an unexposed part is thoroughly dissolved in an aqueous alkali solution, and also to provide a color filter using the photosensitive resin composition. <P>SOLUTION: The photosensitive resin composition for a color filter contains a polymer having a carboxyl group and a (meth)acryloyl group, wherein the polymer is obtained by reacting a carboxylic polymer with a compound having a vinyl ether group and a (meth)acryloyl group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a photosensitive resin composition for a color filter and a color filter. More specifically, the present invention relates to a photosensitive resin composition used for producing a color filter in a liquid crystal display device, a solid-state imaging device or the like, and a color filter formed using the same.

The photosensitive resin composition for a color filter is a photosensitive resin composition (permanent negative resist) used for producing a color filter used for a liquid crystal display element, a solid-state imaging element, and the like, and a radical polymerizable compound, It contains a binder resin, a photo radical initiator, a pigment / pigment dispersant, other additives, a solvent, and the like. A color filter in which such a photosensitive resin composition for a color filter is preferably used is a pixel of at least three primary colors (red (R), green (G), and blue (B)) and a resin black matrix ( BM), a protective film, a columnar spacer, and the like. For example, a photosensitive resin composition for a color filter is applied on a substrate, a pattern is formed by exposure and development through a mask, and baking is performed. After being cured by (baking), it can be produced by a method of applying a protective film or the like.

A conventional photosensitive resin composition for color filters, a photosensitive resin composition for color filters, which contains a photopolymerizable acrylic resin obtained by addition-reaction of a compound having an epoxy group and a (meth) acryloyl group to a carboxyl group-containing resin. The coloring composition is disclosed (for example, refer patent document 1). However, the acrylic resin contained in this composition generates an OH group during the addition reaction, so that the hydrophilicity is improved and the alkali solubility becomes excessive, or the polarity is increased and compatibility with other components is increased. Is not enough. Therefore, when such a composition is used for a color filter, the photocured portion is easily attacked by an alkali developer, and pattern chipping or peeling may occur. In addition, only the resin dissolves first in the unexposed portion. As a result, since pigments, radical polymerizable compounds, and the like remain as residues, there is room for contrivance to obtain a photosensitive resin composition for a color filter having excellent pattern characteristics and development characteristics.
JP-A-9-114095

The present invention has been made in view of the above-described situation, and has high photocurability and can be sufficiently cured with a small exposure amount at the time of curing, and an unexposed portion can be sufficiently dissolved in an alkaline aqueous solution. It is an object of the present invention to provide a photosensitive resin composition for a color filter that can improve the accuracy of the shape and a color filter formed using the same.

The inventors of the present invention have made various studies on the photosensitive resin composition for color filters. When a polymer having a carboxyl group and a (meth) acryloyl group is used as the binder resin, alkali solubility is obtained by the carboxyl group, and radical polymerization is performed. Incorporating components other than the binder resin such as photosensitive compounds and pigments so that development can be performed with an alkaline developer, and radical curability is imparted by the (meth) acryloyl group, thereby improving the sensitivity and strength of the photosensitive resin composition. Since it can be improved, it has been noted that a polymer having both of these groups is useful for forming a color filter. And when such a polymer is obtained by reacting a carboxyl group-containing polymer with a compound having a vinyl ether group and a (meth) acryloyl group, no OH group is produced during the addition reaction, It is found that it is possible to obtain a (meth) acryloyl group-containing polymer having a sufficiently small amount or no OH group, and a photosensitive resin composition for a color filter comprising such a polymer, The inventors have found out that they exhibit excellent pattern characteristics and development characteristics and have come up with the idea that the above problems can be solved brilliantly. In addition, it has been found that a color filter formed using the photosensitive resin composition for a color filter has high performance and high quality due to excellent pattern shape accuracy and the like. It has been reached.

That is, the present invention is a photosensitive resin composition for a color filter comprising a polymer having a carboxyl group and a (meth) acryloyl group, the polymer comprising a carboxyl group-containing polymer, a vinyl ether group, and (meta ) A photosensitive resin composition for a color filter obtained by reacting a compound having an acryloyl group.
The present invention is described in detail below.

In the photosensitive resin composition for color filters of the present invention (hereinafter also referred to as “photosensitive resin composition”), the polymer having a carboxyl group and a (meth) acryloyl group includes a carboxyl group-containing polymer, a vinyl ether. It is obtained by reacting a group and a compound having a (meth) acryloyl group.
Examples of such a polymer having a carboxyl group and a (meth) acryloyl group include a (meth) acryloyl group and a hemiacetal ester group represented by —O—CH (CH ₂ R ³ ) —O—CO—. A group having the following formula, that is, the following general formula (1);

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an organic residue, and R ³ represents a hydrogen atom or an organic residue) ((meth) acryloyl) It is preferable to have a group having a group. In addition, by using a polymer having both such a group and a carboxyl group in the photosensitive resin composition of the present invention, it exhibits a performance excellent in the balance of radical curability, alkali developability and compatibility, and higher A high-resolution pattern can be obtained with sensitivity.

In the general formula (1), examples of the organic residue represented by R ² include a linear, branched or cyclic alkylene group having 2 to 18 carbon atoms, an alkoxyalkylene group having 2 to 20 carbon atoms, C2-C8 halogenated (for example, chlorinated, brominated or fluorinated) alkylene group, polyethylene glycol skeleton excluding terminal hydroxyl group, polypropylene glycol skeleton excluding terminal hydroxyl group, polybutylene glycol skeleton excluding terminal hydroxyl group, aryl group Etc.
Among these, a polyethylene glycol skeleton having a degree of polymerization of 1 to 10,000, a polypropylene glycol skeleton, a polybutylene glycol skeleton, and an alkyl group having 1 to 4 carbon atoms are preferable. More preferably, a polyethylene glycol skeleton having a degree of polymerization of 1 to 100, a polypropylene glycol skeleton, a polybutylene glycol skeleton, an alkylene group having 2 carbon atoms (—CH ₂ CH ₂ —), an alkylene group having 3 carbon atoms (—CH ₂ CH ₂ CH ₂ —), more preferably a polyethylene glycol skeleton, a polypropylene glycol skeleton, or a polybutylene glycol skeleton having a degree of polymerization of 1 to 15.
The organic residue means an organic group bonded to the basic structure constituting the group or compound.

Examples of the organic residue represented by R ³ include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms and an optionally substituted aromatic group having 6 to 11 carbon atoms. Can be mentioned. Among these, a C1-C2 alkyl group is suitable. When one molecule of the compound has a plurality of groups having a (meth) acryloyl group, the organic residues may be the same or different.

The group having a (meth) acryloyl group is a group formed by an addition reaction between a vinyl ether group and a vinyl ether group in a compound having a (meth) acryloyl group and a carboxyl group in a carboxyl group-containing polymer. Preferably it is. In this case, the polymer having a carboxyl group and a (meth) acryloyl group in the present invention has a structure in which the group having the (meth) acryloyl group is bonded to an organic residue formed by the carboxyl group-containing polymer. become.
When a compound having a vinyl ether group and a (meth) acryloyl group is used to form the group having the (meth) acryloyl group, the addition reaction between the vinyl ether group in the compound and the carboxyl group in the carboxyl group-containing polymer is moderated. Since it can carry out on conditions, the group which has a (meth) acryloyl group can be formed easily, without coloring a product.

In addition, the addition reaction between the carboxyl group-containing polymer and the compound having a vinyl ether group and a (meth) acryloyl group is not particularly limited. Either or both may be added to the reaction system continuously or intermittently. In the above addition reaction, since the carboxyl group-containing polymer itself becomes a catalyst, the reaction can be carried out without a catalyst, but a catalyst can also be used in combination. When a catalyst is used in combination, a hydrogen halide such as hydrochloric acid is preferable because the reaction can be accelerated without causing a cationic polymerization reaction.

The amount of the catalyst used may be appropriately set depending on the type or combination of the compound having a vinyl ether group and a (meth) acryloyl group, or a carboxyl group-containing polymer, but the yield, stability of the butterfly, productivity And from the point of economical efficiency, it is preferable to set it as 0.0005-1 weight part with respect to 100 weight part of compounds which have a vinyl ether group and a (meth) acryloyl group, for example. More preferably, it is 0.001-0.5 weight part.

In the present invention, the method for obtaining a polymer having a carboxyl group and a (meth) acryloyl group includes a step of subjecting the carboxyl group-containing polymer and a compound having a vinyl ether group and a (meth) acryloyl group to an addition reaction. For example, (1) In the above addition reaction, the ratio of the carboxyl group-containing polymer and the compound having a vinyl ether group and a (meth) acryloyl group was reacted so that the hydroxyl group remained and remained. A method of introducing a carboxyl group by ring-opening addition of an acid anhydride to a hydroxyl group, (2) In the above addition reaction, a ratio of a carboxyl group-containing polymer and a compound having a vinyl ether group and a (meth) acryloyl group Examples include a method of reacting so that a carboxyl group remains to leave the carboxyl group.

The polymer having a carboxyl group and a (meth) acryloyl group thus obtained preferably has a double bond equivalent (unit: g / eq) of 600 or less. If it exceeds 600, when development is performed with a small exposure amount, curing may be insufficient, and a pattern with higher resolution may not be formed. More preferably, it is 550 or less, More preferably, it is 500 or less. The double bond equivalent is a weight average molecular weight per double bond in a polymer having a carboxyl group and a (meth) acryloyl group.
As the double bond equivalent, for example, a polymer solution for which a double bond equivalent is to be obtained is vacuum-dried at room temperature to obtain a solid content, and then dissolved in deuterated dimethyl sulfoxide together with chloroform as an internal standard substance. ^It can be determined by measuring ¹ H-NMR and quantifying the integral ratio of the double bond peak (δ 5.6 to 6.2, 2H) and the chloroform peak (δ 8.3, 1H).

The polymer preferably has a hydroxyl value (hydroxyl value, unit: mgKOH / g) of 100 or less. If it exceeds 100, the alkali solubility may become excessive, so that the photocured portion is likely to be attacked by the alkali developer, and pattern chipping or peeling may easily occur. Further, the compatibility with other components is not sufficient, and a development residue may be generated. More preferably, it is 90 or less, More preferably, it is 80 or less.

The above polymer further preferably has an upper limit of 200 and a lower limit of 20 as the acid value (unit: mgKOH / g). If it is less than 20, the uncured portion may not be able to be quickly removed with an alkali developer after light irradiation, and it may be difficult to form a highly accurate pattern with good reproducibility. If it exceeds 200, the photocured portion is also easily eroded during alkali development, and similarly, there is a possibility that it is difficult to form a highly accurate pattern with good reproducibility. A more preferred upper limit is 150 and a lower limit is 30. Moreover, as a preferable range, it is 20-200. More preferably, it is 30-150.
In the said polymer, it is preferable to set usage-amounts, such as a compound which has a vinyl ether group and a (meth) acryloyl group, a carboxyl group-containing polymer, so that an acid value may become the said range.

As a weight average molecular weight of the said polymer, it is preferable that an upper limit is 60,000 and a minimum is 3000, for example. If it is less than 3000, heat resistance and thermal stability may not be improved, and if it exceeds 60,000, alkali solubility may not be sufficient. A more preferable upper limit is 50,000 and a lower limit is 4000, and a still more preferable upper limit is 40,000 and a lower limit is 5000. Moreover, as a preferable range, it is 3000-60,000. More preferably, it is 4000-50,000, More preferably, it is 5000-40,000. Moreover, as a ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight measured by GPC (gel permeation chromatography), the upper limit is preferably 4. If it exceeds 4, the thermal stability and alkali solubility may not be sufficient. A more preferred upper limit is 3.5, and a still more preferred upper limit is 3.

In the present invention, the polymer preferably has a double bond equivalent of 600 or less and a hydroxyl value of 100 or less. By forming the photosensitive resin composition for a color filter of the present invention using such a polymer, it becomes possible to further improve pattern characteristics and development characteristics. More preferably, the double bond equivalent is 550 or less and the hydroxyl value is 90 or less.

Below, the compound etc. which are used in order to obtain the said polymer are demonstrated.
The compound having a vinyl ether group and a (meth) acryloyl group in the present invention is not particularly limited, and may be in the form of a monomer, an oligomer (low polymer), or a polymer, and one or more are used. be able to. Examples of such a compound include the following general formula (2);

(In the formula, R ⁴ represents a hydrogen atom or a methyl group. R ⁵ represents an organic residue. R ⁶ represents a hydrogen atom or an organic residue.) (Meth) acrylic acid ester Are preferred.
In the general formula (2), the organic residue represented by R ⁵ is the same as the organic residue represented by R ² , and the organic residue represented by R ⁶ includes R ³ described above. It is the same as the organic residue represented by.

Examples of the (meth) acrylic acid esters represented by the general formula (2) include compounds exemplified below. In addition, these may be used independently and may use 2 or more types together.
(Meth) acrylic acid 2-vinyloxyethyl, (meth) acrylic acid 3-vinyloxypropyl, (meth) acrylic acid 1-methyl-2-vinyloxyethyl, (meth) acrylic acid 2-vinyloxypropyl, (meth) acrylic acid 4 -Vinyloxybutyl, 1-methyl-3-vinyloxypropyl (meth) acrylate, 1-vinyloxymethylpropyl (meth) acrylate, 2-methyl-3-vinyloxypropyl (meth) acrylate, (meth) acrylic acid 1,1-dimethyl-2-vinyloxyethyl, 3-vinyloxybutyl (meth) acrylate, 1-methyl-2-vinyloxypropyl (meth) acrylate, 2-vinyloxybutyl (meth) acrylate, 4- (meth) acrylic acid 4- Vinyloxycyclohexyl, 6-vinyloxyhexyl (meth) acrylate, (meth) acrylic 4-vinyloxymethylcyclohexylmethyl oxalate, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, 2-vinyloxymethylcyclohexylmethyl (meth) acrylate, p-vinyloxymethylphenylmethyl (meth) acrylate, ( (Meth) acrylic acid m-vinyloxymethylphenylmethyl, (meth) acrylic acid o-vinyloxymethylphenylmethyl.

2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (meth) acrylic acid 2- (Vinyloxyethoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyisopropoxy) propyl, (meth) acrylic acid 2- (vinyloxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxy) Ethyl, 2- (vinyloxyethoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate , (Meth) acrylic acid 2- (vinyloxyethoxyethoxy) pro 2- (vinyloxyethoxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) propyl (meth) acrylate 2- (vinyloxyethoxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) isopropyl (meth) acrylate, (meta ) 2- (vinyloxyisopropoxyisopropoxy) isopropyl acrylate, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, (meth) Acrylic acid -(Isopropenoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- ( Isopropenoxyethoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid polyethylene glycol monovinyl ether, (meth) acrylic acid polypropylene glycol monovinyl ether.

Although it does not specifically limit as a carboxyl group-containing polymer in this invention, As a thing with easy acquisition and a synthesis | combination, for example, (1) The homopolymer or copolymer of a carboxyl group-containing monomer, (2) Acid anhydride A polymer obtained by treating a homopolymer or copolymer of a group-containing monomer with a compound having at least one hydroxyl group, (3) a carboxyl group in the homopolymer or copolymer of a carboxyl group-containing monomer Examples thereof include a polymer obtained by reacting a compound having an epoxy group and a (meth) acryloyl group, and one or more of these can be used.

In the carboxyl group-containing polymer of the form (1), examples of the carboxyl group-containing monomer include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and maleic acid monoester. 1 type or 2 or more types such as itaconic acid monoester can be used, among which (meth) acrylic acid is preferred.

In the carboxyl group-containing polymer having the form (2), the homopolymer or copolymer of the acid anhydride group-containing monomer is treated with a compound having at least one hydroxyl group. It is preferably in a form in which a carboxyl group is generated by addition reaction of a compound having at least one group, for example, in the presence of a catalyst and a polymerization inhibitor, the reaction is carried out at a temperature range of 90 to 120 ° C. for 2 to 24 hours. The method is preferably used. Examples of the catalyst include tertiary amines such as triethylamine and dimethylbenzylamine, quaternary ammonium salts such as tetrabutylammonium bromide, phosphines such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, lithium chloride, octyl Metal salts such as zinc acid are preferred, and among them, tertiary amines are most preferred from the viewpoint of reactivity. In addition, when the temperature range is less than 90 ° C., the addition reaction rate is not sufficient, which is economically disadvantageous. When the temperature range exceeds 120 ° C., crosslinking due to thermal polymerization occurs, the molecular weight becomes too high, the gel There is a possibility of becoming.
Examples of the acid anhydride group-containing monomer include one or more of maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like. Acid and itaconic anhydride are preferred.

The compound having at least one hydroxyl group may be in the form of a low molecular weight compound, oligomer, or polymer. For example, methanol, ethanol, propanol, butanol, hexanol, polyethylene glycol monoalkyl ether, polypropylene glycol Monohydric alcohols such as monoalkyl ethers; ethylene glycol, diethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3 -Butanediol, dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-1,4-butanediol 1,7 Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane, 2,2-diethyl-1,3-propane Alkylene oxide addition of diol, 3-methyl-1,4-pentanediol, 2,2-diethyl-1,3-butanediol, 4,5-nonanediol, triethylene glycol, hydrogenated bisphenol A, hydrogenated bisphenol A , Alkylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, trimethylol ethane, trimethylol propane, glycerin, polyglycerin, pentaerythritol, dipentaerythritol and other polyhydric alcohols; sorbitol, xyl Sugars such as tall, xylylose, glucose, fructose, mannitol; hydroxyl group-containing polycondensates such as unsaturated polyester, saturated polyester, epoxy acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate 2-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, allyl alcohol, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, p-hydroxystyrene, butene-2-diol-1, Polymers having a hydroxyl group such as 4; cellulose, starch, dextran; one or more of phenolic compounds such as phenol, cresol and bisphenol can be used. Of these, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferred.

In the carboxyl group-containing polymer in the form (3) above, a compound having an epoxy group and a (meth) acryloyl group is reacted with a part of the carboxyl group of the homopolymer or copolymer of the carboxyl group-containing monomer. It is preferable to be in a form in which the compound is subjected to addition reaction with a part of the carboxyl group, for example, in the presence of a catalyst and a polymerization inhibitor, the reaction is performed at a temperature range of 90 to 120 ° C. for 2 to 24 hours. The method is preferably used. Examples of the catalyst include tertiary amines such as triethylamine and dimethylbenzylamine, quaternary ammonium salts such as tetrabutylammonium bromide, phosphines such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, lithium chloride, octyl Metal salts such as zinc acid are preferred, and among them, tertiary amines are most preferred from the viewpoint of reactivity. In addition, when the temperature range is less than 90 ° C., the addition reaction rate is not sufficient, which is economically disadvantageous. When the temperature range exceeds 120 ° C., crosslinking due to thermal polymerization occurs, the molecular weight becomes too high, the gel There is a possibility of becoming.

As the homopolymer or copolymer of the carboxyl group-containing monomer, the carboxyl group-containing polymer having the form (1) is preferable.
Moreover, as a compound which has an epoxy group and a (meth) acryloyl group, any form of a low molecular weight compound, an oligomer, and a polymer may be sufficient, for example, glycidyl (meth) acrylate, (meth) acrylic acid 3, Epoxycyclohexyl derivatives of (meth) acrylic acid such as 4-epoxycyclohexylmethyl; alicyclic epoxy derivatives of (meth) acrylate; one or more of β-methylglycidyl (meth) acrylate can be used. . Of these, glycidyl (meth) acrylate is preferred.

In the above carboxyl group-containing polymer, examples of the monomer used when copolymerizing a carboxyl group-containing monomer or an acid anhydride group-containing monomer include, for example, methyl (meth) acrylate and (meth) acrylic. (Meth) acrylates such as ethyl acetate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate ) Acrylic acid esters; Styrenes such as styrene, p-methylstyrene, α-methylstyrene; Vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl butyrate; N-vinylacetamide, N-vinylformamide, N- Vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-bi N- vinyl compounds such as carbazole, methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether, ethylene, propylene, may be used alone or two or more of such olefins such butylene.

As a polymerization method of the monomer component in the carboxyl group-containing polymer, for example, polymerization is preferably performed using a radical polymerization initiator, and a chain transfer agent may be used as necessary to adjust the molecular weight. it can. Further, polymerization can be carried out by bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization, emulsion polymerization, or a method of appropriately combining these. Among these, it is preferable to perform polymerization by solution polymerization. Moreover, although it can carry out by a batch type or a continuous type, it is preferable to use a batch type.

Examples of the radical polymerization initiator include cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-butylperoxy- Organic peroxides such as 2-ethylhexanoate and t-amylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexanecarbonitrile) 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl-2,2′-azobis (2-methylpropionate), dimethyl-2,2′-azobis (2-methylpropionate) 1 type, or 2 or more types, such as azo compounds, etc. can be used. What is necessary is just to set suitably as the usage-amount according to the combination of the monomer component to be used, reaction conditions, etc.

Examples of the molecular weight regulator include thiol chain transfer agents such as n-dodecanethiol, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, and α-methylstyrene dimer. It is preferable to use n-dodecanethiol, 3-mercaptopropionic acid, and methyl 3-mercaptopropionate because they are high, can reduce residual monomers, and are easily available.
As a method for adding the chain transfer agent to the reaction vessel, a continuous charging method such as dropping or divided charging can be applied. Further, the chain transfer agent may be introduced alone into the reaction vessel, or may be mixed in advance with a monomer component, a solvent or the like.

In the above polymerization method, a solvent may be used as necessary, but as the solvent, those used in usual radical polymerization reaction can be used. For example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc. Esters; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; one or two of chloroform, dimethyl sulfoxide, and the like More than seeds can be used. Of these, ethers, ketones and esters are preferred. More preferred are propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate. It is preferable to use the same kind of such a polymerization solvent and the organic solvent used for the photosensitive resin composition for color filters described later.
As the usage-amount of the said polymerization solvent, it is preferable that it is 5-500 mass% with respect to 100 mass% of all the monomer components used, for example. More preferably, it is 50-200 mass%.

In the above polymerization method, the monomer component, radical polymerization initiator and the like are added to the reaction vessel by charging all of the monomer components into the reaction vessel and adding the radical polymerization initiator into the reaction vessel. Method of copolymerization; Method of carrying out copolymerization by charging a part of the monomer component into the reaction vessel and adding the radical polymerization initiator and the remaining monomer component into the reaction vessel; Polymerization solvent in the reaction vessel And a method of adding the whole amount of the monomer component and the radical polymerization initiator is suitable. Among these, since the molecular weight distribution of the obtained polymer can be narrowed (sharpened) and the reaction can be easily controlled, the radical polymerization initiator and the monomer component are successively dropped into the reaction vessel. It is preferable to carry out copolymerization by a method, and it is preferable to add a radical polymerization initiator even after dropping of the monomer components since the residual monomer can be reduced.

In the above polymerization method, the conditions for the polymerization reaction may be appropriately set depending on the polymerization method used, the solvent, the radical polymerization initiator, the chain transfer agent, etc. For example, the polymerization temperature should be 50 to 150 ° C. Is preferred. When the temperature is lower than 50 ° C., it is necessary to use an initiator having a low decomposition temperature, which may be disadvantageous for industrial production, for example, a facility for cooling and storing the initiator is required. If it exceeds 200 ° C., the monomer component may start to undergo thermal polymerization before reaching the decomposition temperature of the initiator. More preferably, it is 80-150 degreeC. The reaction time is preferably 0.5 to 24 hours.

The photosensitive resin composition for a color filter of the present invention essentially comprises the polymer having the carboxyl group and the (meth) acryloyl group, and if necessary, a radical polymerizable compound and a photo radical initiator. (Photopolymerization initiator), a colorant, a dispersant, and other additives can be included. In such a photosensitive resin composition for a color filter, it is formed on the substrate of the color filter and exposed to light, whereby the excellent physical properties and alkali developability of the polymer and a radical polymerizable compound are formed. The dimensional network structure can form a cured film having excellent physical properties such as adhesion to the surface of the substrate to be coated (substrate surface), film strength, heat resistance, temperature-resistant pure water, and chemical resistance. When the pattern is exposed and developed, an accurate pattern can be formed.

As content of the said polymer to occupy in the photosensitive resin composition of this invention, it is preferable that an upper limit is 70 mass% and a minimum is 1 mass%. If it is out of this range, there is a possibility that sufficient coating strength and developability cannot be obtained, and coating may be difficult. A more preferred upper limit is 60% by mass and a lower limit is 3% by mass. A more preferred upper limit is 50% by mass, and a lower limit is 5% by mass. Moreover, as a preferable range, it is 1-70 mass%. More preferably, it is 3-60 mass%, More preferably, it is 5-50 mass%.

In the photosensitive resin composition, the radical polymerizable compound is capable of curing by a photopolymerization reaction. For example, a radical polymerizable oligomer in the form of an oligomer (low polymer) or a monomer (monomer) ) Is preferably used. Examples of the radical polymerizable oligomer include unsaturated polyester, epoxy acrylate, urethane acrylate, polyester acrylate, and an acrylic polymer having a double bond in the side chain. Examples of the radical polymerizable monomer include aromatic vinyl monomers such as styrene, α-methylstyrene, α-chlorostyrene, vinyl toluene, divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; vinyl such as vinyl acetate and vinyl adipate. Ester monomers; (meth) acrylate monomers such as methyl (meth) acrylate, 2-hydroxymethyl (meth) acrylate, (2-oxo-1,3-dioxolan-4-yl) -methyl (meth) acrylate; (di) Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, Intererythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Examples thereof include polyfunctional (meth) acrylates such as acrylate, dipentaerythritol hexa (meth) acrylate, and tris (hydroxyethyl) isocyanurate, such as tri (meth) acrylate; triallyl cyanurate. Among these, it is preferable to use a polyfunctional (meth) acrylate from the viewpoints of the photosensitive performance and developability of the resulting photosensitive resin composition, the physical properties of the coating film after post-baking, and the like. In addition, these may be used independently and may use 2 or more types together.

As for the usage-amount of the said radically polymerizable compound, it is preferable that an upper limit is 1000 weight part and a minimum is 10 weight part with respect to 100 weight part of polymers which have the said carboxyl group and (meth) acryloyl group. If it is less than 10 parts by weight, the curing power at the time of exposure may not be sufficient, and if it exceeds 1000 parts by weight, the effects of other components may not be sufficiently exhibited. A more preferred upper limit is 600 parts by weight and a lower limit is 20 parts by weight, and a more preferred upper limit is 400 parts by weight and a lower limit is 30 parts by weight.

The photo radical initiator is excited by actinic rays to generate radicals, and initiates polymerization of the radical polymerizable compound. For example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and alkyl ethers thereof Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as phenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1; Acylphosphine oxides; One or more of xanthones can be used.

As for the usage-amount of the said photoradical initiator, it is preferable that an upper limit is 50 weight part and a minimum is 0.1 weight part with respect to 100 weight part of said radically polymerizable compounds. If the amount is less than 0.1 parts by weight, it may be necessary to increase the light irradiation time, or polymerization may not occur sufficiently even if light irradiation is performed, and appropriate developability may not be obtained. If it exceeds 50 parts by weight, the coating film may be colored, the strength may not be sufficient, and it may be economically disadvantageous. A more preferred upper limit is 40 parts by weight and a lower limit is 0.5 parts by weight, a still more preferred upper limit is 30 parts by weight, and a lower limit is 1 part by weight.

In addition, a thermal polymerization initiator can be used in combination with the photo radical initiator.
The thermal polymerization initiator is not particularly limited. For example, cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t- Organic peroxides such as butylperoxy-2-ethylhexanoate and t-amylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis ( Azo compounds such as cyclohexanecarbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate); Can be used. What is necessary is just to set suitably as the usage-amount of a thermal-polymerization initiator in the range which does not impair the effect of this invention.

Examples of the colorant include dyes and pigments, and it is preferable to use pigments.
Examples of the pigment include C.I. among organic compounds classified as pigments in a color index (CI: issued by The Society of Dyer's and Colorists). I. Pigment Yellow 24, 31, 53, 83, 138, C.I. I. Pigment Orange 43, C.I. I. Pigment Red 105, 176, 177, 254, C.I. I. Pigment Violet 14, 29, C.I. I. Pigment Blue 15, 15: 6, 22, 28, C.I. I. Pigment Green 15, 25, 36, C.I. I. Pigment Brown 28, C.I. I. Organic pigments such as Pigment Black 1 and 7; one or two of inorganic pigments such as metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, or complex oxides More than seeds can be used.
With respect to the amount of the colorant used, the upper limit is 400 parts by weight and the lower limit is 1 part by weight with respect to a total of 100 parts by weight of the polymer having the carboxyl group and (meth) acryloyl group and the radical polymerizable compound. Preferably there is. A more preferred upper limit is 300 parts by weight, and a lower limit is 5 parts by weight. A more preferred upper limit is 200 parts by weight, and a lower limit is 10 parts by weight.

As the dispersant, for example, one or more of surfactants, pigment intermediates, dye intermediates, polymer dispersants and the like can be used. Examples of the surfactant include polyethylene glycol alkyl ethers such as polyethylene glycol lauryl ether and polyethylene glycol stearyl ether; polyethylene glycol aryl ethers such as polyethylene glycol octyl phenyl ether and polyethylene glycol nonyl phenyl ether; polyethylene glycol dilaurate, polyethylene glycol Polyethylene glycol diesters such as distearate; Fluorine surfactants such as BM-1000 (manufactured by BM Heavy); Cationic surfactants such as organosiloxane polymers; Anionic polymer high molecular unsaturated polycarboxylics Examples include anionic surfactants such as acids. As the intermediate of the pigment and the intermediate of the dye, for example, a derivative of an organic dye in which a substituent is introduced into the organic dye as a base is preferable. Examples of the organic dye as a base include azo series, phthalocyanine series, quinacridone series, anthraquinone series, perylene series, thioindigo series, dioxazine series, metal complex series, etc., and substituents include hydroxyl group, carboxyl group, sulfone group, Examples thereof include a carbonamide group and a sulfonamide group.
Such a dispersant is preferably used in combination with the above-mentioned colorant. The amount used is 100 parts by weight of the colorant, and the upper limit is 50 parts by weight and the lower limit is 0.1 parts by weight. Is preferred. A more preferred upper limit is 30 parts by weight and a lower limit is 0.5 parts by weight, a still more preferred upper limit is 20 parts by weight and a lower limit is 1 part by weight, a most preferred upper limit is 10 parts by weight and a lower limit is 1 part by weight.

Other additives include aluminum hydroxide, talc, clay, barium sulfate and other fillers, antifoaming agents, coupling agents, leveling agents, sensitizers, mold release agents, lubricants, plastics as necessary. An agent, an antioxidant, an ultraviolet absorber, a flame retardant, a polymerization inhibitor, a thickener, and the like can be used. Moreover, you may mix | blend epoxy resins, such as a novolak-type epoxy resin, a bisphenol-type epoxy resin, an alicyclic epoxy resin, a triglycidyl isosinurate, dicyandiamide, an imidazole compound, or a dioxazoline compound. What is necessary is just to set these addition amounts suitably in the range which does not impair the effect of this invention.

The photosensitive resin composition may be diluted with a diluent as necessary. As the diluent, the above radical polymerizable compound or a suitable solvent can be used. The solvent is the same as the polymerization solvent in the above-described polymerization method, and the amount used thereof may be appropriately set according to the optimum viscosity when using the photosensitive resin composition. For example, the photosensitive resin The upper limit is preferably 1000 parts by weight and the lower limit is preferably 10 parts by weight with respect to 100 parts by weight of the composition.

It does not specifically limit as a manufacturing method of the photosensitive resin composition for color filters of this invention, For example, in addition to the said polymer, as needed, a radically polymerizable compound, a photoradical initiator (photoinitiator), It can be produced by a method in which a coloring agent, a dispersing agent, other additives, and the like are mixed or added to a solvent and stirred to uniformly dissolve and disperse. Note that the mixing order and the like are not particularly limited. Examples of the apparatus used for stirring include a paint shaker, a bead mill, a sand grind mill, a ball mill, an attritor mill, a two roll mill, and a three roll mill.

This invention is also a color filter formed using the said photosensitive resin composition for color filters.
Here, the color filter is composed of at least three primary color (RGB) pixels, a resin black matrix, a protective film, a columnar spacer, and the like. In the present invention, at least one of these structural members is included. What is necessary is just to be formed using the said photosensitive resin composition, and using for at least 3 primary color (RGB) pixel is suitable. More preferably, all the color filter members are produced using the photosensitive resin composition.
In the above color filter member, as the photosensitive resin composition of the present invention, in the case of forming three primary color (RGB) pixels, each of the three primary color pigments of red, green, and blue is contained and used. When forming a black matrix, a black pigment is contained and used. Moreover, when using for a protective film or a columnar spacer, it is not necessary to contain a pigment.
Such a color filter member can be formed, for example, by sequentially performing the following steps (1) to (3).

(1) The photosensitive resin composition for a color filter of the present invention is coated on a transparent substrate such as glass, preferably non-alkali glass or transparent plastic by a method such as spin coating or spraying, and then dried. A coating film is prepared. As a coating method, a spin coating method is preferable. In the drying conditions, the temperature is preferably room temperature to 120 ° C. More preferably, the temperature is 60 ° C to 100 ° C. The drying time is preferably 10 seconds to 60 minutes. More preferably, it is 30 seconds to 10 minutes. Furthermore, it is preferable to heat and dry under normal pressure or vacuum.
(2) Then, a photomask (patterning film) provided with an opening corresponding to the desired pattern shape is placed on the coating film prepared in (1) in a contact state or a non-contact state and irradiated with light. To cure. As light, radiation such as ultraviolet rays, X-rays, and electron beams is preferable in addition to visible light. More preferably, it is ultraviolet rays. Note that a high-pressure mercury lamp is preferably used as the ultraviolet ray source.

(3) After light irradiation, development is performed with a solvent, water, an alkaline aqueous solution, or the like. Among these, it is preferable to use an alkaline aqueous solution because it can carry out highly sensitive development with little burden on the environment. As the alkali component, for example, potassium hydroxide, sodium hydroxide, sodium carbonate and the like are suitable. The alkali concentration is preferably 0.01 to 5% by mass. If it is less than 0.01% by mass, the photosensitive resin composition may not have sufficient solubility. If it exceeds 5% by mass, the dissolving power becomes too strong to obtain excellent developability. There is a fear. More preferably, it is 0.05-3 mass%. Further, a surfactant may be further added to the alkaline aqueous solution.
Since the coating film formed from the photosensitive resin composition of the present invention is excellent in tack-free properties even before exposure, it can be easily peeled even when a photomask is placed in contact. The pattern can be reproduced accurately.

In the case of forming a color filter constituent member, after the steps (1) to (3), heating is further performed (post-bake) to advance the curing, and the remaining solvent is completely removed. Is preferred. Thereby, the radically polymerizable double bond in the photosensitive resin composition that has not been cured by exposure can be sufficiently cured to form a very strong crosslinked body, and the coating film strength can be further improved. . The curing temperature during post-baking is preferably 120 to 300 ° C. If it is lower than 120 ° C, curing may not proceed sufficiently and the coating film strength may not be excellent. If it is higher than 300 ° C, there is a risk of coloring, and the coating film may be thermally decomposed. There is a possibility that the smoothness of the film will not be sufficient. More preferably, it is 150-250 degreeC, More preferably, it is 180-230 degreeC. Note that the post-baking may be performed after development in forming each member, or may be performed after all the members are formed.

As a color filter, first, the steps (1) to (3) are performed using a photosensitive resin composition containing a black pigment, and after forming a resin black matrix on the substrate, the pigment is red (R). , Green (G), and blue (B) are sequentially changed to repeat the steps (1) to (3) to form R, G, and B pixels, thereby producing RGB pixels. Thereafter, a protective film may be formed in order to protect the RGB pixels formed on the substrate and improve the smoothness of the surface. The color filter protective film can be formed using a known thermosetting resin or photocurable resin. However, from the viewpoint of the coating film strength, smoothness, and low colorability of the protective film, the photosensitive film of the present invention is used. It is preferable to use a conductive resin composition. Further, when the color filter is a color filter for a liquid crystal display device, it is preferable to form a columnar spacer. The columnar spacer can be produced by applying the photosensitive resin composition on the surface on which the spacer is to be formed to a thickness that is the height of the desired spacer, and then performing the steps (1) to (3). .

The color filter of the present invention thus obtained can be suitably used for a liquid crystal display device, a display device using an organic EL, or the like. Hereinafter, a case where a color filter is used in the liquid crystal display device will be described.
The liquid crystal display device includes a liquid crystal between the color filter and, if necessary, a color filter substrate provided with an ITO electrode and an alignment film, and a counter substrate provided with an alignment film, an ITO electrode, and a drive element as necessary. The liquid crystal display device incorporates a liquid crystal display panel that displays a color by maintaining a constant interval with a spacer, enclosing a liquid crystal substance in the interval, changing the orientation of the liquid crystal by an electric signal, and changing the light transmittance. The operation mode and driving method of the liquid crystal are not particularly limited, but the TFT method is preferable from the viewpoint of display quality, response speed, and the like.

As the liquid crystal spacer, a well-known fine particle spacer, a columnar spacer using a photosensitive resin, or the like can be used. Among them, a columnar spacer formed using the photosensitive resin composition for a color filter of the present invention is preferably used. . The color filter substrate and the counter substrate are preferably provided with an alignment film having an alignment according to the operation mode and driving method of each liquid crystal, and further, if necessary, a fine protrusion (rib), and a polyimide alignment film is preferable. Used for. Moreover, the photosensitive resin composition for color filters of this invention other than a polyimide can be used for a rib. Furthermore, it is preferable to dispose a deflection plate and an optical compensation film according to the operation mode and driving method of each liquid crystal outside the color filter substrate and the counter substrate.

Since the photosensitive resin composition for color filters of the present invention has the above-described configuration, it is highly photocurable and can be sufficiently cured with a small exposure amount during curing, and the unexposed portion can be sufficiently dissolved in an alkaline aqueous solution. Since the accuracy of the pattern shape after development can be improved, it is useful as a material for forming the three primary color pixels, the resin black matrix, the protective film, the columnar spacer, etc. in the color filter.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “% by mass”.
The weight average molecular weight, acid value / hydroxyl value, and double bond equivalent in the examples were determined as follows.
(Weight average molecular weight)
GPC apparatus HLC-8220GPC (manufactured by Tosoh Corp.) was used as a measuring apparatus, and tetrahydrofuran was used as a developing solvent, and measurement was performed in terms of polystyrene.
(Acid value / Hydroxyl value)
The measurement was performed according to JIS K 0070.
(Double bond equivalent)
The polymer solution is vacuum-dried at room temperature to obtain a solid content, dissolved in deuterated dimethyl sulfoxide together with chloroform as an internal standard substance, ¹ H-NMR is measured, and the double bond peak and the chloroform peak are integrated. Calculated from the ratio.

Synthesis example 1
A separable flask with a cooling tube was prepared as a reaction vessel, charged with 750 parts of diethylene glycol dimethyl ether (DMDG), purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. .
On the other hand, as a monomer dropping tank, 250 parts of benzyl methacrylate (BzMA), 65 parts of methyl methacrylate (MMA), 185 parts of methacrylic acid (MAA), t-butylperoxy-2-ethylhexanoate (PBO; A product prepared by adding 10 parts of Nippon Oil & Fats, trade name “Perbutyl O”) and stirring and mixing it well was prepared, and 22.5 parts of n-dodecanethiol (n-DM) was put into a beaker as a chain transfer agent dropping tank I prepared something.
After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel, and polymerization was started. While maintaining the temperature at 90 ° C., the dropwise addition was performed over 180 minutes, and the temperature increase was started 30 minutes after the completion of the dropwise addition to bring the reaction vessel to 110 ° C. After maintaining at 110 ° C. for 90 minutes, it was cooled to room temperature.
As an inhibitor, 1.2 parts of 2,2′-methylenebis (4-methyl-6-tert-butylphenol) (MBMTB) was added, a gas introduction tube was attached to a separable flask, and oxygen / nitrogen = 5/95 (v / v ) Bubbling of mixed gas was started. While the reaction vessel was cooled in a water bath, 267 parts of 2- (vinyloxyethoxy) ethyl methacrylate (VEEM) was added dropwise over 3 hours. Remove the water bath, raise the temperature of the reaction vessel to 40 ° C. with an oil bath, continue stirring at 40 ° C. for 3 hours, cool to room temperature, and then dilute with 400 parts of DMDG to give a polymer with a solid content of 40%. A solution was obtained. Table 1 shows the weight average molecular weight, acid value, double bond equivalent, and hydroxyl value of the obtained polymer.

Synthesis example 2
Prepare a separable flask with a cooling tube as a reaction vessel, charge 817 parts of DMDG and 153 parts of maleic anhydride, purge with nitrogen, and then heat in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. did.
On the other hand, as a dropping tank, 197 parts of styrene and 17.5 parts of PBO were placed in a beaker and well stirred and mixed.
After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the dropping vessel and polymerization was started. While maintaining the temperature at 90 ° C., dropping was performed over 150 minutes, and after 60 minutes from the completion of dropping, the temperature was raised to 110 ° C. The temperature was maintained at 110 ° C. for 90 minutes, and then cooled to 90 ° C.
MBMTB 1.2 parts was added as an inhibitor, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started. 219 parts of 2-hydroxyethyl acrylate and 2.3 parts of triethylamine (TEA) were added, reacted at 90 ° C. for 3 hours, and then cooled to room temperature. While cooling the reaction vessel in a water bath, 201 parts of 2- (vinyloxyethoxy) ethyl acrylate was added dropwise over 3 hours. Remove the water bath, raise the temperature of the reaction vessel to 40 ° C. with an oil bath, continue stirring at 40 ° C. for 3 hours, cool to room temperature, dilute with 300 parts of DMDG, and polymer with a solid content concentration of 40% A solution was obtained. Table 1 shows the weight average molecular weight, acid value, double bond equivalent, and hydroxyl value of the obtained polymer.

Synthesis example 3
A separable flask equipped with a cooling tube was prepared as a reaction vessel, and 750 parts of DMDG was charged and purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C.
On the other hand, 250 parts of BzMA, 50 parts of MMA, 200 parts of MAA, and 10 parts of PBO were put into a beaker as a monomer dropping tank, and a well-stirred and mixed one was prepared. Got ready.
After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel, and polymerization was started. While maintaining the temperature at 90 ° C., the dropwise addition was performed over 180 minutes. Temperature increase was started 30 minutes after the dropping was completed, and the reaction vessel was brought to 110 ° C.
90 minutes after reaching 110 ° C., 1.2 parts of MBMTB was added as an inhibitor, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started. 140 parts of glycidyl methacrylate (GMA) and 2.3 parts of TEA were added, reacted at 110 ° C. for 8 hours, and then cooled to room temperature. While cooling the reaction vessel with a water bath, 105 parts of VEEM was added dropwise over 3 hours. Remove the water bath, raise the temperature of the reaction vessel to 40 ° C. with an oil bath, continue stirring at 40 ° C. for 3 hours, cool to room temperature, and then dilute with 370 parts of DMDG to give a polymer with a solid content of 40%. A solution was obtained. Table 1 shows the weight average molecular weight, acid value, double bond equivalent, and hydroxyl value of the obtained polymer.

Synthesis example 4
A separable flask equipped with a cooling tube was prepared as a reaction vessel, and 750 parts of DMDG was charged and purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C.
On the other hand, as a monomer dropping tank, 250 parts of BzMA, 70 parts of MMA, 180 parts of MAA, and 10 parts of PBO were put in a beaker and well stirred and mixed, and 22.5 parts of n-DM was put in a beaker as a chain transfer agent dropping tank. I prepared something.
After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel, and polymerization was started. While maintaining the temperature at 90 ° C., the dropwise addition was performed over 180 minutes. Temperature increase was started 30 minutes after the dropping was completed, and the reaction vessel was brought to 110 ° C.
90 minutes after reaching 110 ° C., 1.1 parts of MBMTB was added as an inhibitor, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started. 186 parts of GMA and 2.1 parts of TEA were added, reacted at 110 ° C. for 8 hours, and then cooled to room temperature. Dilution was performed with 280 parts of DMDG to obtain a polymer solution having a solid concentration of 40%. Table 1 shows the weight average molecular weight, acid value, double bond equivalent, and hydroxyl value of the obtained polymer.

Synthesis example 5
A separable flask equipped with a cooling tube was prepared as a reaction vessel, and 750 parts of DMDG was charged and purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C.
On the other hand, 250 parts of BzMA, 105 parts of MMA, 145 parts of MAA, and 10 parts of PBO were put in a beaker as a monomer dropping tank, and a well-stirred and mixed one was prepared. Got ready.
After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel, and polymerization was started. While maintaining the temperature at 90 ° C., the dropwise addition was performed over 180 minutes. Temperature increase was started 30 minutes after the dropping was completed, and the reaction vessel was brought to 110 ° C.
90 minutes after reaching 110 ° C., 1.0 part of MBMTB was added as an inhibitor, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started. 140 parts of GMA and 2.0 parts of TEA were added and reacted at 110 ° C. for 8 hours, and then cooled to room temperature. Dilution was performed with 210 parts of DMDG to obtain a polymer solution having a solid concentration of 40%. Table 1 shows the weight average molecular weight, acid value, double bond equivalent, and hydroxyl value of the obtained polymer.

<Photosensitive resin composition for color filter>
Example 1-1
Using the polymer solution obtained in Synthesis Example 1 as the polymer solution, mixing according to the blending ratio shown in Table 2 to prepare a red, green, blue, black colored resin composition and a transparent resin composition, It filtered using a 1 micrometer filter.
The red, green and blue colored resin compositions and the transparent resin composition were applied on a non-alkali glass plate using a spin coater so that the thickness after drying would be 2 μm, and 80 mm on a hot plate. Dry at 5 ° C. for 5 minutes. Next, ultraviolet rays were irradiated through a mask having line and space portions at intervals of 10 μm with an ultrahigh pressure mercury lamp so that the irradiation amount was 100 mJ / cm ² .
About the black coloring resin composition, it apply | coated on the alkali free glass plate so that the thickness after drying might be set to 1 micrometer using a spin coater, and it dried for 5 minutes at 80 degreeC with the hotplate. Next, ultraviolet rays were irradiated through a mask having line-and-space portions with an interval of 10 μm with an ultrahigh pressure mercury lamp so that the irradiation amount was 300 mJ / cm ² .
The unirradiated portion was dissolved and removed with 0.05% aqueous potassium hydroxide solution, rinsed with pure water for 1 minute, then observed with an optical microscope, and the pattern property and development residue were evaluated. Any colored resin composition and transparent Also in the resin composition, the shape of the ultraviolet irradiated portion (residual pattern) was good, and no development residue was found in the unirradiated portion.

Example 1-2
Except that the polymer solution obtained in Synthesis Example 2 was used as the polymer solution, the patternability and development residue were evaluated in the same manner as in Example 1-1, and any colored resin composition and transparent resin were evaluated. Also in the composition, the shape of the ultraviolet irradiated portion (residual pattern) was good, and no development residue was found in the unirradiated portion.

Example 1-3
Except that the polymer solution obtained in Synthesis Example 3 was used as the polymer solution, the patternability and development residue were evaluated in the same manner as in Example 1-1, and any colored resin composition and transparent resin were evaluated. Also in the composition, the shape of the ultraviolet irradiated portion (residual pattern) was good, and no development residue was found in the unirradiated portion.

Comparative Example 1-1
Except that the polymer solution obtained in Synthesis Example 4 was used as the polymer solution, the patternability and the development residue were evaluated in the same manner as in Example 1-1. As a result, any colored resin composition and transparent resin were evaluated. Also in the composition, the ultraviolet irradiation part (residual pattern) had chipping or peeling, and a development residue was seen in the unirradiated part.

Comparative Example 1-2
Except that the polymer solution obtained in Synthesis Example 5 was used as the polymer solution, the patternability and development residue were evaluated in the same manner as in Example 1-1, and any colored resin composition and transparent resin were evaluated. Also in the composition, the ultraviolet irradiation part (residual pattern) had chipping or peeling, and a development residue was seen in the unirradiated part.

The descriptions in Table 2 are as follows.
Red Pigment Dispersion: Pigment Red 254 Dispersion Green Pigment Dispersion: Pigment Green 36 + Pigment Yellow 138 (weight ratio 6: 4) Dispersion Blue Pigment Dispersion: Pigment Blue 15: 6 Dispersion DPHA: Dipentaerythritol Hexaacrylate Irg907: Irgacure 907 (trade name, manufactured by Ciba Specialty Chemicals)
PGMEA: Propylene glycol monomethyl ether acetate

From Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-2, when a polymer having a double bond equivalent of 600 or less and a hydroxyl value of 100 or less is used, the pattern property and the development residue are further increased. It turned out to be good.

<Color filter>
Example 2
The transparent resin composition obtained in Example 1-2 using the red, green, blue, and black resin compositions obtained in Example 1-2 as the colored resin composition, and the resin composition for protective films and spacers. A color filter was prepared and evaluated as follows.
A black resin composition was applied to a 300 mm × 400 mm non-alkali glass substrate by a spin coating method to form a coating film, and prebaked (80 ° C., 5 minutes). After that, alignment exposure is performed through a predetermined black matrix photomask at an exposure amount of 500 mJ / cm ² using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source, and development is performed with an alkaline developer. Then, post-baking (230 ° C., 30 minutes) was performed to form a black matrix (thickness: 1.2 μm).
Next, the red resin composition was applied onto the substrate on which the black matrix was formed by spin coating to form a coating film, and prebaked (80 ° C., 5 minutes). After that, alignment exposure is performed through a predetermined photomask for pixels at an exposure amount of 100 mJ / cm ² using a proximity exposure machine using an ultrahigh pressure mercury lamp as a light source, development is performed with an alkaline developer, and pure water is used. After washing, post-baking (200 ° C., 30 minutes) was performed to form a red pixel pattern (thickness 2.0 μm). Similarly, a green pixel pattern was formed using the green resin composition, and a blue pixel pattern was formed using the blue resin composition.

A protective film resin composition was applied onto the substrate on which the black matrix and each color pixel were formed by spin coating to form a coating film, and prebaked (80 ° C., 5 minutes). Thereafter, alignment exposure is performed through a predetermined photomask for protective film using a proximity exposure machine using an ultrahigh pressure mercury lamp as a light source at an exposure amount of 100 mJ / cm ² , development is performed with an alkaline developer, and pure water is used. Then, post-baking (200 ° C., 30 minutes) was performed to form a protective film (thickness 1.5 μm).
The spacer resin composition was applied by spin coating on the substrate on which the protective film was formed to form a coating film, and prebaked (80 ° C., 5 minutes). After that, alignment exposure is performed through a predetermined photomask for spacers using a proximity exposure machine using an ultrahigh pressure mercury lamp as a light source at an exposure amount of 100 mJ / cm ² , development is performed with an alkaline developer, and pure water is used. After washing, post-baking (220 ° C., 30 minutes) was performed to form spacers (height 4.8 μm, bottom 12 μm × 12 μm square).
When the produced color filter was inspected with an optical microscope, there was no pattern defect and no development residue, and it was good.

Comparative Example 2
As the colored resin composition, the red, green, blue and black resin compositions obtained in Comparative Example 1-1 were used, and the transparent resin composition obtained in Comparative Example 1-1 was used as the protective film and spacer resin composition. A color filter was prepared and evaluated in the same manner as in Example 2 except that it was used. As a result, pattern defects and development residues were observed in the color filter.

Claims (2)

A photosensitive resin composition for a color filter comprising a polymer having a carboxyl group and a (meth) acryloyl group,
A photosensitive resin composition for a color filter, wherein the polymer is obtained by reacting a carboxyl group-containing polymer with a compound having a vinyl ether group and a (meth) acryloyl group. A color filter formed using the photosensitive resin composition for a color filter according to claim 1.