JP5133658B2 - Photosensitive resin composition for black matrix, cured product and color filter using the same - Google Patents

Description

  The present invention relates to a photosensitive resin composition that can be cured by irradiation with ultraviolet rays or an electron beam and can be patterned by alkali development, and a color filter using the same, and more particularly, a photosensitive resin suitable as a resist for a black matrix. The present invention relates to a functional resin composition.

  A color liquid crystal display device has a liquid crystal part for controlling the amount of light transmitted or reflected and a color filter as components, and the manufacturing method of the color filter is usually applied to the surface of a transparent substrate such as glass or plastic sheet. A method is used in which a black matrix (black matrix) is formed, and then different hues of red, green, and blue are sequentially formed in a color pattern such as a stripe shape or a mosaic shape. In recent years, color liquid crystal display devices have been used in various fields such as liquid crystal televisions, liquid crystal monitors, and color liquid crystal mobile phones, and color filters are one of the important components that influence the visibility of these color liquid crystal display devices. is there. The pattern size varies depending on the use of the color filter and each color, but the red, green and blue pixels are thinned from 100 μm to 50 μm or less, and the black matrix is thinned from 20 μm to 10 μm or less. Therefore, the photosensitive resin composition for obtaining a color filter is required to form a pattern with high dimensional accuracy.

  Generally, a photosensitive resin composition for such an application includes a polyfunctional photocurable monomer having a polymerizable unsaturated bond, an alkali-soluble binder resin, a photopolymerization initiator, and the like. .

  For example, Japanese Patent Application Laid-Open No. 61-213213 (Patent Document 1) and Japanese Patent Application Laid-Open No. 1-152449 (Patent Document 2) exemplify application as a material for a color filter, and has a carboxyl group as a binder resin ( Copolymers of (meth) acrylic acid or (meth) acrylic acid esters, maleic anhydride and other polymerizable monomers are disclosed. However, since the copolymer disclosed here is a random copolymer, an alkali dissolution rate distribution occurs in the light irradiated part as well as in the light non-irradiated part, and the margin during the developing operation is narrow. In addition, it is difficult to obtain an acute pattern shape or a fine pattern. In particular, when a high concentration of pigment is included, the exposure sensitivity is remarkably lowered, and a fine negative pattern cannot be obtained. JP-A-4-340965 (Patent Document 3) discloses that an alkali-soluble unsaturated compound having a polymerizable unsaturated double bond and a carboxyl group in one molecule can form a negative pattern such as a color filter. It is disclosed that it is effective. Since molecules having alkali solubility are insolubilized by light irradiation, it is predicted that the sensitivity will be higher than the combination of the binder resin and the polyfunctional polymerizable monomer described above, but the compounds exemplified here are Acrylic acid and acid anhydride, which are polymerizable unsaturated bonds, are arbitrarily added to the hydroxyl group of the phenol oligomer, and even in such a proposal, the distribution of the alkali dissolution rate is due to the heterogeneity of the molecular composition. It is difficult to form a wide and fine negative pattern.

  On the other hand, JP-A-4-345673 (Patent Document 4), JP-A-4-345608 (Patent Document 5), JP-A-4-355450 (Patent Document 6), and JP-A-4-363311 ( Patent Document 7) discloses a liquid resin using a reaction product of an epoxy (meth) acrylate having a bisphenolfluorene structure and an acid anhydride. However, the resins exemplified by them have a low molecular weight because they are reaction products of epoxy (meth) acrylate and acid monoanhydride. Therefore, the sensitivity of the compound is low and a fine pattern cannot be formed.

  JP-A-5-339356 (Patent Document 8), JP-A-5-146132 (Patent Document 9), and WO94 / 00801 pamphlet (Patent Document 10) disclose a dihydroxypropyl acrylate compound and an acid dianhydride. An alkali-developable unsaturated resin composition obtained by copolymerization with acid or an alkali-developable unsaturated resin composition obtained by copolymerization of acid monoanhydride and acid dianhydride with a dihydroxypropyl acrylate compound is disclosed. In this case, the copolymerization of the acid dianhydride and the dihydroxypropyl acrylate compound proceeds to obtain an oligomer. However, since the number of polymerizable unsaturated bonds in the repeating unit is constant, the crosslinking density cannot be improved, and it may be difficult to form a fine line pattern under a high concentration pigment, and there is room for improvement. .

Furthermore, JP-A-9-325494 (Patent Document 11) increases the molecular weight of the carboxyl group-containing copolymer to carry out polyfunctionalization of the alkali-soluble resin composition. However, in this case as well, the crosslinking density cannot be improved because the number of polymerizable unsaturated bonds in the repeating unit is constant as in the above-mentioned patent document.
JP 61-213213 Japanese Unexamined Patent Publication No. 1-152449 Japanese Unexamined Patent Publication No. 4-340965 JP-A-4-345673 JP-A-4-345608 JP-A-4-355450 Japanese Unexamined Patent Publication No. 4-363311 JP-A-5-339356 JP-A-5-146132 WO94 / 00801 pamphlet JP-A-9-325494

  Therefore, as a result of intensive studies to solve the problems in the conventional photosensitive resin composition as described above, the present inventors have found that a diol compound containing a polymerizable unsaturated group and a tetracarboxylic acid or an acid diacid thereof. By reacting a carboxyl group-containing copolymer obtained by reacting with an anhydride with an epoxy compound containing a polymerizable unsaturated bond group, and further reacting with a dicarboxylic acid or its acid monoanhydride, a photosensitive resin is obtained. It has been found that an alkali-soluble resin suitable for forming a composition can be obtained. By using this alkali-soluble resin, the crosslink density is improved while controlling the solubility in alkali developer, the difference in solubility between the hardened part and the uncured part in the alkaline developer is increased, and fine line patterns are formed beautifully. In addition, it has succeeded in obtaining a photosensitive resin composition having high sensitivity and a wide development adhesion margin.

  Accordingly, an object of the present invention is to provide a photosensitive resin composition for a black matrix that is excellent in forming a fine pattern even when a light-shielding pigment having a high concentration is added, and is suitable as a black matrix material for a high light-shielding or high-definition color filter. It is to provide.

  Another object of the present invention is to provide a cured product and a color filter obtained by using the photosensitive resin composition.

（ただし、Ｒ₁、Ｒ₂、Ｒ₃、及びＲ₄は、独立に水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を示し、Ｒ₅は水素原子又はメチル基を示す。また、Xは-CO-、-SO₂-、-C(CF₃)₂-、-Si(CH₃)₂-、-CH₂-、-C(CH₃)₂-、-O-、9,9-フルオレニレン基又は直結合を示し、Yは４価のカルボン酸残基を示す。Gは重合性二重結合とカルボキシル基を有する置換基を示す。Zは下記一般式（２）で表される置換基を示し、ｎは１〜２０の数を表す。）

（但し、Lは２または３価のカルボン酸残基を示し、pは１または２である）
（ii）少なくとも1個以上のエチレン性不飽和結合を有する光重合性モノマー、
（iii）光重合開始剤、及び
（iv）遮光性顔料
を必須の成分として含有することを特徴とするブラックマトリックス用感光性樹脂組成物である。 That is, the present invention provides (i) an alkali-soluble resin represented by the following general formula (1) and having a carboxylic acid residue and a polymerizable unsaturated group in one molecule;

_{(Wherein, R 1, R 2, R} 3, and R ₄ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group. X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9 , 9-fluorenylene group or a direct bond, Y represents a tetravalent carboxylic acid residue, G represents a substituent having a polymerizable double bond and a carboxyl group, and Z is represented by the following general formula (2). And n represents a number of 1 to 20.)

(However, L represents a divalent or trivalent carboxylic acid residue, and p is 1 or 2.)
(Ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
A photosensitive resin composition for a black matrix comprising (iii) a photopolymerization initiator and (iv) a light-shielding pigment as essential components.

  Moreover, this invention is the hardened | cured material obtained by hardening the said photosensitive resin composition.

  Furthermore, this invention is the color filter formed of the hardened | cured material obtained by apply | coating the said photosensitive resin composition and making it harden | cure.

Hereinafter, the photosensitive resin composition of the present invention will be described in detail.
The photosensitive resin composition of the present invention is a resin composition having properties as an alkali developing photosensitive resin composition containing an alkali-soluble resin represented by the general formula (1) as a main component. The alkali-soluble resin represented by the general formula (1) has a photopolymerizable unsaturated group derived from a diol compound having (meth) acrylic acid, and thus has radical polymerizability, as well as dicarboxylic acid or its acid monoanhydride. And has an acid solubility derived from tetracarboxylic acid or acid dianhydride, and thus has alkali solubility.

  The alkali-soluble resin represented by the general formula (1) is obtained by reacting (meth) acrylic acid with an epoxy compound having two glycidyl ether groups derived from bisphenols, to obtain a diol compound having a polymerizable unsaturated group. Obtained by reacting a tetracarboxylic acid or its acid dianhydride, reacting the resulting reaction product with an oxirane compound containing a polymerizable double bond, and further reacting with a dicarboxylic acid or its acid monoanhydride. It is a carboxyl group-containing alternating copolymer. Since the alkali-soluble resin of the general formula (1) has both a polymerizable unsaturated double bond and a carboxyl group, it gives excellent photocurability, good developability, and patterning characteristics to the alkali-developable photosensitive resin composition. The physical properties of the protective film, light shielding film, red, green, and blue pixels are improved.

The method for producing the alkali-soluble resin represented by the general formula (1) will be described in detail. First, the alkali-soluble resin of the general formula (1) is an epoxy compound having two glycidyl ether groups derived from bisphenols, particularly preferably an epoxy compound represented by the general formula (3) and (meth) acrylic acid. It is derived from a diol compound containing a polysynthetic unsaturated group obtained by the reaction.

In the above general formula (3), R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, preferably a hydrogen atom. , An alkyl group having 1 to 5 carbon atoms, or a phenyl group, and more preferably a hydrogen atom. X represents —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —Si (CH ₃ ) ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, 9 , 9-fluorenylene group or a direct bond, preferably 9,9-fluorenylene group. Here, the 9,9-fluorenylene group refers to a group represented by the following general formula (4).

Such a reaction between the epoxy compound and (meth) acrylic acid can be carried out using a known method, for example, using about 2 moles of (meth) acrylic acid per mole of the epoxy compound. The reactant obtained by this reaction is described in, for example, Patent Document 6 mentioned above. The reaction product obtained by this reaction is a diol compound containing a polymerizable unsaturated group, and is an epoxy (meth) acrylate compound represented by the following general formula (6).

  Preferred bisphenols that give the alkali-soluble resin of the general formula (1) include the following. Bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4 -Hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) Hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4- Hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) Methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2 , 2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, Bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether and the like. In addition, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4- Hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4- Hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, etc. are also preferred Can be mentioned. Furthermore, 4,4′-biphenol, 3,3′-biphenol and the like are also preferred.

The alkali-soluble resin of the general formula (1) can be obtained from an epoxy compound derived from bisphenols as described above. In addition to such an epoxy compound, a phenol novolac type epoxy compound, a cresol novolak type epoxy compound, and the like are also available. Any compound that significantly contains a compound having two glycidyl ether groups can be used. Further, when bisphenols are glycidyl etherified, oligomer units represented by the following general formula (5) are mixed, and the average value of m in the general formula (5) is 0 to 10, preferably 0. If it is in the range of ˜2, there is no problem in the performance of the resin composition.

（ただし、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｘ、Ｙ及びＧは上記一般式（１）の場合と同じである。また、Ｒ₆は２価のアルキレン基、Ｒ₇は水素原子またはメチル基を示し、Ｚは上記一般式（２）で表される置換基を示す。更に、ｎは１〜２０の数であり、ｐは一般式（２）の場合と同じであり、ｑは０または１の数を示す。） Next, a general formula (9) by reaction of a diol compound containing a polymerizable unsaturated group, a tetracarboxylic acid or an acid dianhydride thereof, an oxirane compound containing a polymerizable unsaturated group, and a dicarboxylic acid or an acid monoanhydride thereof. A method for producing the alkali-soluble resin of the present invention represented by 1) will be described. An example of the method for producing the alkali-soluble resin of the present invention is shown in the following reaction formula (I).

(However, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , X, Y and G are the same as those in the general formula (1). R ₆ is a divalent alkylene group, R ₇ Represents a hydrogen atom or a methyl group, Z represents a substituent represented by the general formula (2), n represents a number of 1 to 20, and p is the same as in the general formula (2). And q represents a number of 0 or 1.)

  Regarding the above reaction formula (I), first, the epoxy (meth) acrylate compound (diol containing a polymerizable unsaturated group) of the above general formula (6) obtained by the reaction of the aforementioned epoxy compound with (meth) acrylic acid. Compound) and an acid component are reacted to obtain a compound represented by the general formula (7) (reactant having a carboxyl group). There are no particular restrictions on the reaction conditions such as the solvent and catalyst used at this time. For example, a solvent having no hydroxyl group and having a boiling point higher than the reaction temperature is preferably used as the reaction solvent. Cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high boiling point ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, cyclohexanone, diisobutyl ketone, etc. It may be a ketone solvent or the like. The catalyst used may be a known catalyst such as ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine. it can. These are described in detail in the aforementioned Patent Document 11. Moreover, as an acid component, it is good to use the acid dianhydride (B) which can react with the hydroxyl group in an epoxy (meth) acrylate compound molecule | numerator. This acid component is effective either saturated or unsaturated. Among these, as acid dianhydride (B), acid dianhydride of saturated linear hydrocarbon tetracarboxylic acid, acid dianhydride of alicyclic tetracarboxylic acid, acid dianhydride of aromatic tetracarboxylic acid, etc. Can be used.

  Here, examples of the acid dianhydride of the saturated linear hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid dianhydride, and the like. It may be an acid dianhydride of a saturated cyclic tetracarboxylic acid substituted with a cyclic hydrocarbon.

  In addition, as the acid dianhydride of alicyclic tetracarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid dianhydride, etc. Furthermore, the acid dianhydride of the alicyclic tetracarboxylic acid by which the saturated hydrocarbon was substituted may be sufficient. Examples of the acid dianhydride of aromatic tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and diphenylsulfone tetracarboxylic acid dianhydride. it can. The acid dianhydride in the present invention is preferably an acid dianhydride of biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, or biphenyl ether tetracarboxylic acid, and more preferably an acid dianhydride of biphenyl tetracarboxylic acid or biphenyl ether tetracarboxylic acid. It is a thing. Two or more of these acid dianhydrides can be used in combination.

  A method for producing a compound represented by the general formula (7) by reacting an epoxy (meth) acrylate compound with an acid component is not particularly limited. For example, as described in Patent Document 11 above, A known method such as reacting an epoxy (meth) acrylate compound with tetracarboxylic dianhydride at a reaction temperature of 90 to 140 ° C. can be employed. Preferably, the diol compound (A) having a polymerizable unsaturated group represented by the general formula (6) and the acid dianhydride (B) so that the terminal of the compound represented by the general formula (7) is a hydroxyl group. It is desirable to make the reaction quantitatively so that the molar ratio [(B) / (A)] to 50) is less than 100 mol%. When the molar ratio is less than 50 mol%, the content of the unreacted epoxy (meth) acrylate compound is increased, and there is a concern that the stability over time of the alkali-soluble resin composition is lowered. On the other hand, when the molar ratio is 100 mol% or more, the terminal of the compound represented by the general formula (7) becomes an acid anhydride, and the content of unreacted acid dianhydride increases and the oxirane compound is added later. There are concerns about side reactions during the reaction. The reaction temperature is preferably 90 to 130 ° C. and the raw materials are uniformly dissolved and reacted, followed by reaction and aging at 40 to 80 ° C.

  Subsequently, the compound represented by the general formula (7) is reacted with the oxirane compound (C) to obtain the compound represented by the general formula (8) [reactant having a hydroxyl group]. The oxirane compound (C) is a compound containing one or more polymerizable double bonds and one oxirane ring, such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3 1, 4-epoxycyclohexyl methacrylate and the like.

  About the manufacturing method of the compound represented by General formula (8), it does not specifically limit, The general reaction conditions of addition reaction of carboxylic acid and an epoxy compound can be used. In addition, as described in the above-mentioned Patent Document 11, an epoxy compound and (meth) acrylic acid that react bisphenolfluorene type epoxy resin and acrylic acid at 100 ° C. using tetraethylammonium bromide or the like as a catalyst. The manufacturing method of the epoxy (meth) acrylate compound by reaction with can also be referred. The reaction temperature for synthesizing the compound represented by the general formula (8) is preferably in the range of 40 to 120 ° C, more preferably 40 to 90 ° C. The molar ratio of the oxirane compound (C) when synthesizing the compound represented by the general formula (8) is the acid dianhydride (B) used in the reaction of the compound represented by the general formula (7). In other words, the molar ratio [(C) / (B)] is preferably 160 to 220 mol%. When the molar ratio is less than 160 mol%, part of the ester bond derived from the acid dianhydride in the compound represented by the general formula (8) becomes a half ester due to the presence of the unreacted carboxylic acid. There is a concern that the molecular weight may decrease due to the regeneration reaction of the acid anhydride. On the other hand, when the molar ratio exceeds 220 mol%, there is a concern about the change over time of the alkali-soluble resin represented by the general formula (1) due to a side reaction or the like derived from the unreacted oxirane compound.

  Subsequently, the hydroxyl group of the compound represented by the general formula (8) is reacted with the acid monoanhydride (D) to obtain an alkali-soluble resin represented by the general formula (9). Here, as the acid monoanhydride (D), an acid anhydride of a saturated linear hydrocarbon dicarboxylic acid, an acid anhydride of a saturated cyclic hydrocarbon dicarboxylic acid, an acid anhydride of an aromatic dicarboxylic acid, or the like may be used. it can. Among these, examples of the acid anhydride of the saturated linear hydrocarbon dicarboxylic acid include succinic acid, acetyl succinic acid, adipic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelin. Examples thereof include anhydrides such as acid, sebacic acid, suberic acid, and diglycolic acid, and may also be linear hydrocarbon dicarboxylic acid anhydrides substituted with hydrocarbon groups. Examples of acid anhydrides of saturated cyclic hydrocarbon dicarboxylic acids include acid anhydrides such as hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, and hexahydrotrimellitic acid. Further, an acid anhydride of an alicyclic dicarboxylic acid substituted with a saturated hydrocarbon may be used. Examples of the acid anhydride of unsaturated dicarboxylic acid include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, and trimellitic acid. Among these, the acid monoanhydride (D) is preferably succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, trimellitic anhydride, more preferably succinic acid, itaconic. Acid, tetrahydrophthalic acid anhydride. In addition, it cannot be overemphasized that the alkali-soluble resin represented by General formula (9) is an example of the alkali-soluble resin represented by General formula (1).

  The reaction temperature when synthesizing the compound represented by the general formula (9) by reacting the hydroxyl group of the compound represented by the general formula (8) with the acid monoanhydride (D) is 20 to 120 ° C. The range is preferably 40 to 90 ° C. The molar ratio of the acid monoanhydride (D) when synthesizing the compound represented by the general formula (9) is such that the diol compound (A) having the polymerizable unsaturated group, the acid dianhydride (B), and the oxirane. For the formula (2 × ((A)-(B)) + (C)) converted from the number of moles (mol) of the compound (C), that is, the molar ratio [(D) / [2 [(A) -(B) + (C)]]] is preferably 20 to 110 mol%. The molar ratio of the acid monoanhydride can be arbitrarily changed within the above range for the purpose of adjusting the acid value of the alkali-soluble resin represented by the general formula (1).

An example of the method for producing the general formula (1) will be specifically described in the case where 9,9-bis (4-hydroxyphenyl) fluorene is used as a starting material.
First, 9,9-bis (4-hydroxyphenyl) fluorene and epichlorohydrin are reacted to synthesize a bisphenolfluorene type epoxy compound represented by the following general formula (10). A bisphenolfluorene type epoxy (meth) acrylate resin represented by the following general formula (11) is synthesized by reacting with (meth) acrylic acid represented by CH ₂ = CHR ₅ -COOH (R ₅ is the same as above). To do. Next, this bisphenol fluorene type epoxy (meth) acrylate resin is reacted with acid dianhydride (B), oxirane compound (C), and acid monoanhydride (D) sequentially while heating in a solvent such as propylene glycol monomethyl ether acetate. Thus, the alkali-soluble resin of the general formula (1) is obtained.

  The photosensitive resin composition for black matrix of the present invention contains the alkali-soluble resin represented by the general formula (1) as a main component of the resin component. Here, the resin component refers to a component that becomes a resin by polymerization or curing, and includes an oligomer and a monomer in addition to the resin. Further, “containing as a main component” means that the alkali-soluble resin represented by the general formula (1) is contained in the resin component at 30 wt% or more, preferably 50 wt% or more, more preferably 60 wt% or more. The photosensitive resin composition of the present invention may contain an alkali-soluble resin represented by the general formula (1) as an essential component, and components other than the resin of the general formula (1) may be resin components, And non-resin components such as fillers and colorants.

  In order to take advantage of the characteristics of the photosensitive resin composition for black matrix, the following components (i), (ii), (iii) and (iv) are contained as essential components. (I) an alkali-soluble resin having a carboxylic acid group and a polymerizable unsaturated group in one molecule represented by the general formula (1), and (ii) a photopolymerization having at least one ethylenically unsaturated bond. A basic monomer, (iii) a photopolymerization initiator, and (iv) a light-shielding pigment.

  Among these, as the photopolymerizable monomer having at least one ethylenically unsaturated bond as the component (ii), for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Monomers having a hydroxyl group such as ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pen Pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate of a (meth) acrylic acid esters. These compounds can be used alone or in combination of two or more thereof.

  The blending ratio [(i) / (ii)] of the component (ii) and the alkali-soluble resin [component (i)] represented by the general formula (1) is 20/80 to 90/10. Preferably 40/60 to 80/20. When the blending ratio of the alkali-soluble resin is small, the cured product after photocuring becomes brittle, and the acid value of the coating film is low in the unexposed area, so that the solubility in an alkali developer is lowered and the pattern edge is distorted. The problem of not getting sharp will occur. On the contrary, when the blending ratio of the alkali-soluble resin is larger than the above range, the ratio of the photoreactive functional group in the resin is small and the formation of the crosslinked structure is not sufficient, and the acid value in the resin component is too high, Since the solubility with respect to the alkaline developer in the exposed portion is increased, there is a possibility that the formed pattern becomes thinner than the target line width or the pattern is easily lost.

  Examples of the photopolymerization initiator of component (iii) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyl. Acetophenones such as acetophenone, benzophenone, 2-chlorobenzophenone, benzophenones such as p, p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2- (o-chlorophenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5-diphenyl Biimidazole, 2- (o-methoxyphenyl) ) -4,5-diphenylbiimidazole, biimidazole compounds such as 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloro Halomethylthiazole compounds such as methyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloroRmethyl) -1,3,5-triazine, 2- ( 4-methoxystyryl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- ( Halomethyl-s-triazine compounds such as 4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 1,2-octanedione, 1- [4- (phenylthio) phenyl ]-, 2- (o-benzoyloxime), 1- (4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime-o-benzoate, 1- (4-methylsulfanylphenyl) butane-1 , 2-dione-2-oxime-o-acetate, 1- (4-methylsulfanylphenyl) butan-1-oneoxime-o-acetate, etc., o-acyloxime compounds, benzyldimethyl ketal, thioxanthone, 2-chloro Thioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxone Organic compounds such as sulfur compounds such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, anthraquinones such as 2,3-diphenylanthraquinone, azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, etc. Products, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine. One or more of these photopolymerization initiators can be used.

  The amount of photopolymerization initiator used as component (iii) is based on a total of 100 parts by weight of the alkali-soluble resin [component (i)] and photopolymerizable monomer [component (ii)] represented by the general formula (1). 2 to 50 parts by weight, preferably 15 to 40 parts by weight. When the blending ratio of the photopolymerization initiator as the component (ii) is small, the speed of photopolymerization becomes slow and the sensitivity is lowered. On the other hand, if the number is too large, the sensitivity is too strong and the pattern line width becomes thicker than the pattern mask, and the line width that is faithful to the mask cannot be reproduced, or the pattern edge does not rattle and become sharp. Problems may arise. Incidentally, the photopolymerization initiator (iii) includes those having a photosensitizing action, but it is possible to add a photosensitizer separately.

  In addition, examples of the light-shielding pigment of component (iv) include black organic pigments, mixed-color organic pigments, and light-shielding materials. Among these, examples of the black organic pigment include perylene black and cyanine black. Examples of mixed color organic pigments include those obtained by mixing at least two pigments selected from red, blue, green, purple, yellow, cyanine, magenta and the like into a pseudo black color. Examples of the light shielding material include carbon black, chromium oxide, iron oxide, titanium black, aniline black, and cyanine black. Two or more types can be appropriately selected and used. The surface smoothness, dispersion stability, and compatibility with the resin are preferable.

  The light-shielding pigment as component (iv) can be used together with a dispersant as necessary. Examples of such a dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether. The amount of the light-shielding pigment as the component (iv) is 30 to 280 parts by weight, preferably 50 to 230 parts by weight with respect to 100 parts by weight of the total amount of the alkali-soluble resin represented by the general formula (1) and the component (ii). Good range of parts. If it is less than these ranges, the light shielding properties will not be sufficient, and in order to obtain a desirable light shielding rate, it will be necessary to increase the film thickness, making it difficult to obtain the surface smoothness of the color filter. On the other hand, if the amount is too large, the dispersion stability of the photosensitive resin composition for the black matrix is lowered, and the content of the photosensitive resin as the original binder is also reduced. There is a possibility that an undesirable problem of damage occurs.

  The essential components are (i) the alkali-soluble resin represented by the general formula (1), (ii) the photopolymerizable monomer, (iii) the photopolymerization initiator, and (iv) the light-shielding pigment. The photosensitive resin composition for black matrix contained as is useful as a black matrix material for color filters. These can be dissolved in a solvent as necessary, or various additives can be used in combination. That is, when the photosensitive resin composition of the present invention is used for a color filter or the like, it is preferable to use a solvent in addition to the above essential components. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2- Ketones such as pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene Glycol ethers such as glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Examples include acetates such as ether acetate, and the like, and these can be dissolved and mixed to form a uniform solution-like composition.

  Further, the black matrix photosensitive resin composition of the present invention is blended with additives such as a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a leveling agent, and an antifoaming agent, as necessary. be able to. Among these, examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl. Examples of the filler include glass fiber, silica, mica, and alumina. Examples of the antifoaming agent and leveling agent include silicon-based, fluorine-based, and acrylic compounds.

  The photosensitive resin composition for black matrix of the present invention is represented by the general formula (1) of (i) in a solid content excluding a solvent (the solid content includes a monomer that becomes a solid content after curing). It is desirable that the alkali-soluble resin, (ii) the photopolymerizable monomer, (iii) the photopolymerization initiator, and (iv) the light-shielding pigment contain 70 wt% or more, preferably 80 wt%, more preferably 90 wt% or more in total. . The amount of the solvent varies depending on the target viscosity, but is preferably in the range of 20 to 80 wt% with respect to the total amount.

  In addition, the coating film (cured product) of the present invention is, for example, coated with a solution of the photosensitive resin composition on a substrate or the like, dried, irradiated with light (including ultraviolet rays, radiation, etc.), and cured. Can be obtained. A coating film having a desired pattern can be obtained by providing a portion that is exposed to light and a portion not exposed to light, curing only the portion that is exposed to light, and dissolving the other portion with an alkaline solution.

  Next, the manufacturing method of the color filter using the photosensitive resin composition is demonstrated. First, after applying the photosensitive resin composition on the surface of the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Next, this coating film is exposed through a photomask, and then developed using an alkaline developer to dissolve and remove the unexposed portions of the coating film, and then post-baked to define the portions where pixels are to be formed. A black matrix formed as described above is obtained.

  When applying the photosensitive resin composition to the substrate, any method such as a method using a roller coater machine, a land coater machine, or a spinner machine can be adopted in addition to a known solution dipping method and spray method. . After applying to a desired thickness by these methods, the film is formed by removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, a hot plate, etc., vacuum drying, or a combination thereof. The heating temperature and heating time in the pre-baking are appropriately selected according to the solvent used, and for example, the heating is performed at a temperature of 80 to 120 ° C. for 1 to 10 minutes.

  As the radiation used when producing the black matrix, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be used, and radiation having a wavelength in the range of 250 to 450 nm is preferable. . Examples of the developer suitable for the alkali development include, for example, an aqueous solution of an alkali metal or alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like. It is better to develop at a temperature of 20-30 ° C. using a weakly alkaline aqueous solution containing 0.05-10% by weight of carbonate such as lithium carbonate, and a fine image using a commercially available developing machine or ultrasonic cleaner. Can be formed precisely. In addition, it is usually washed with water after alkali development. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 10 to 120 seconds at room temperature.

  After the development as described above, a heat treatment (post-bake) is performed at a temperature of 180 to 250 ° C. and a condition of 20 to 100 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned coating film and the substrate. This is performed by heating with an oven, a hot plate or the like, as in the pre-bake. The patterned coating film of this invention is formed through each process by the above photolithography method.

  Examples of the substrate used for forming the black matrix include glass and transparent films (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.). In addition, these substrates are optionally subjected to appropriate pretreatments such as application of a transparent electrode layer, chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc. It can also be applied.

  Since the photosensitive resin composition for black matrix of the present invention contains an alkali-soluble resin represented by the general formula (1), it has higher solubility in an alkali developer than conventional ones, and ethylene in one molecule. Since the number of polymerizable unsaturated bond groups is large, the crosslinking density after curing is high. That is, since the difference in solubility in the alkaline developer between the cured portion and the uncured portion after irradiation with ultraviolet rays or electron beams is increased, a fine pattern can be formed even in a thin film or at a high colorant concentration. Therefore, the photosensitive resin composition for black matrix of the present invention is particularly suitable as a color filter protective film material and a black matrix forming material. The color filter thus obtained is extremely useful for, for example, a transmissive, reflective, or transflective color liquid crystal display device, a color imaging tube element, a color sensor, and the like.

  Below, this invention is demonstrated further in detail based on the synthesis example etc. of alkali-soluble resin represented by General formula (1). The scope of the present invention is not limited by these synthesis examples. Moreover, evaluation of the resin in the following synthesis examples was performed as follows unless otherwise noted.

[Solid content]
1 g of the resin solution (including reaction products and alkali-soluble resins) obtained in the synthesis examples (and comparative synthesis examples) was impregnated into a glass filter [weight: W ₀ (g)] and weighed [W ₁ (G)] and the weight [W ₂ (g)] after heating for 2 hours at 160 ° C.
Solid content concentration (% by weight) = 100 × (W ₂ −W ₀ ) / (W ₁ −W ₀ )

[Acid value]
The resin solution was dissolved in dioxane and titrated with a 1/10 N-KOH aqueous solution using phenolphthalein as an indicator.

[Molecular weight]
This is a value obtained by calculating the weight average molecular weight (Mw) as a standard polystyrene conversion value by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.

Abbreviations used in the synthesis examples and comparative synthesis examples are as follows.
FHPA: Equivalent reaction product of bisphenolfluorene type epoxy resin and acrylic acid (manufactured by Nippon Steel Chemical Co., Ltd., ASF-400 solution: solid content concentration 50wt%, solid content converted acid value 1.28mgKOH / g)
FHPPA: Equivalent reaction product of bis (phenylphenol) fluorene type epoxy resin and acrylic acid (50wt% PGMEA solution, solid content equivalent acid value 7.51mgKOH / g)
BisA-GEA: Equivalent reaction product of bisphenol A diglycidyl ether and acrylic acid (50wt% PGMEA solution, acid value 1.72mgKOH / g in solid content)
BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride
BTDA: 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride
ODPA: 3,3 ', 4,4'-oxydiphenyltetracarboxylic dianhydride
CHDA: 3,3 ', 4,4'-oxydiphenyltetracarboxylic dianhydride
THPA: 1,2,3,6-tetrahydrophthalic anhydride
HHPA: Hexahydrophthalic anhydride
GMA: Glycidyl methacrylate
HBAGE: 4-hydroxybutyl acrylate glycidyl ether
TEAB: Tetraethylammonium bromide
TPP: Triphenylphosphine
PGMEA: Propylene glycol monomethyl ether acetate

[Synthesis Example 1]
In a 1000 ml four-necked flask with a reflux condenser, 600.00 g (0.49 mol) of a 50% PGMEA solution of FHPA [component (A)], 72.75 g (0.247 mol) of BPDA [component (B)], and 39.56 PGMEA 1.30 g of g and TPP were charged, stirred at 120 to 125 ° C. with heating for 2 hours, and further heated and stirred at 70 to 75 ° C. for 6 hours to obtain a reaction product (a). The solid content concentration of the obtained reaction product (a) was 52.4 wt%, the acid value (converted to solid content) of the resin was 78.0 mgKOH / g, and the weight average molecular weight (Mw) by GPC analysis was 3400.

  Next, 73.92 g (0.52 mol) of GMA [component (C)] was charged into the reaction product (a), and the mixture was stirred at 80 ° C. for 8 hours to be reacted. Further, 156.71 g (1.03 mol) of THPA [component (D)] was charged into the flask and stirred at 80 ° C. for 7 hours to synthesize an alkali-soluble resin (i) -1. The obtained alkali-soluble resin had a solid content of 62.0 wt%, an acid value (in terms of solid content) of 111.8 mg KOH / g, and Mw of 3700 by GPC analysis. In addition, the (A)-(D) component names and blending ratios used for the synthesis of the alkali-soluble resin (i) -1 according to Synthesis Example 1, and the weight-average molecular weight of the obtained alkali-soluble resin (i) -1 The acid values are collectively shown in Table 1 (the same applies to the following synthesis examples).

[Synthesis Example 2]
The reaction was conducted in the same manner as in Synthesis Example 1 except that the amount of THPA [component (D)] in Synthesis Example 1 was changed to 118.68 g (0.78 mol) to obtain an alkali-soluble resin (i) -2. .

[Synthesis Example 3]
In a 1000 ml four-necked flask equipped with a reflux condenser, 600.00 g (0.49 mol) of a 50% PGMEA solution of FHPA (A), 96.02 g (0.33 mol) of BPMDA (component (B)), 4.36 g of PGMEA, and TEAB was added in an amount of 1.02 g, and the mixture was stirred at 120 to 125 ° C. for 2 hours with heating, and further heated and stirred at 60 to 65 ° C. for 8 hours to obtain a reaction product (b). The obtained reaction product (b) had a solid content concentration of 57.8 wt%, an acid value (converted to a solid content) of 91.6 mg KOH / g, and Mw by GPC analysis of 8800.

  Next, 93.82 g (0.66 mol) of GMA [component (C)] was charged into the reaction product (b), and the mixture was stirred at 80 ° C. for 24 hours to be reacted. Furthermore, 153.67 g (1.01 mol) of THPA [(D) component] and 153.67 g of PGMEA were charged into the flask and stirred at 80 ° C. for 24 hours to synthesize an alkali-soluble resin (i) -3. The obtained alkali-soluble resin had a solid content concentration of 59.2 wt%, an acid value (in terms of solid content) of 126.8 mgKOH / g, and Mw of 6800 by GPC analysis.

[Comparative Synthesis Example 1]
In a 500 ml four-necked flask with a reflux condenser, 206.26 g (0.17 mol) of a 50% PHPEA solution of FHPA, 0.085 mol of BPDA, 0.085 mol of THPA, 26.0 g of PGMEA and 0.45 g of TPP are charged, 120 to 125 The mixture was stirred for 6 hours while heating at 0 ° C. to obtain Resin (i) -4. The obtained resin solution had a solid content concentration of 55.6 wt%, an acid value (in terms of solid content) of 103.0 mg KOH / g, and Mw by GPC analysis of 2600.

[Comparative Synthesis Example 2]
In a 1000 ml four-necked flask equipped with a reflux condenser, 600.00 g (0.49 mol) of 50% PHPEA solution of FHPA, 96.02 g (0.33 mol) of BPDA, 4.36 g of PGMEA, and 1.02 g of TEAB are charged, 120 to 125 The mixture was stirred for 2 hours with heating at 0 ° C., and further stirred with heating at 60 to 65 ° C. for 8 hours to obtain Resin (i) -5. The obtained resin solution had a solid content concentration of 58.5 wt%, an acid value (converted to solid content) of 91.0 mgKOH / g, and Mw by GPC analysis of 8600.

  Next, the present invention will be specifically described based on Examples and Comparative Examples relating to black matrix production, but the present invention is not limited to these. Here, the raw materials and abbreviations used in the production of the black matrix of the following examples and comparative examples are as follows.

(i) -1 component: the alkali-soluble resin obtained in Synthesis Example 1 above
(i) -2 component: the alkali-soluble resin obtained in Synthesis Example 2 above
(i) -3 component: the alkali-soluble resin obtained in Synthesis Example 3 above
(i) -4 component: the alkali-soluble resin obtained in Comparative Synthesis Example 1 above
(i) -5 component: the alkali-soluble resin obtained in Comparative Synthesis Example 2 above
(ii) -1 Component: Dipentaerythritol hexaacrylate
(ii) -2 Ingredients: Trimethylolpropane triacrylate
(iii) -1 component: oxime ester photopolymerization initiator (Irgacure OXE02, manufactured by Ciba Specialty Chemicals)
(iii) -2 component: Benzophenone photopolymerization initiator (manufactured by Ciba Specialty Chemicals, Irgacure 369)
(iv) -1 component: carbon dispersion having a pigment concentration of 20.0% and a total solid content of 24% (average particle size of 100 to 130 nm)
(iv) -2 component: carbon dispersion having a pigment concentration of 20.0% and a total solid content of 29% (average particle size of 100 to 150 nm)
Solvent-1: Propylene glycol monomethyl ether acetate solvent-2: Cyclohexanone additive-1: Silane coupling agent (SH-6040 manufactured by Toray Dow Corning)

  The above-described blending components were blended in the proportions shown in Table 2 to prepare black resist photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4. The numerical values in Table 2 all represent parts by weight.

[Examples 1 to 6 and Comparative Examples 1 to 4]
The photosensitive resin composition for black resist shown in Table 2 was applied on a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after post-baking was 0.9 to 1.0 μm, and 1 at 80 ° C. Pre-baked for a minute to prepare a coated plate. Then, the photocuring reaction of the photosensitive part was performed by irradiating ultraviolet rays with an illumination intensity of 100 mJ / cm ² with a wavelength of 365 nm with a 500 W / cm ² high pressure mercury lamp. Next, this exposed coated plate is developed in a 0.04 wt% potassium hydroxide aqueous solution or 0.5 wt% sodium carbonate aqueous solution by a shower development at 24 ° C., and further developed for 30 seconds, and further washed with spray water. The unexposed part of the coating film was removed. Then, the heat drying process was performed for 30 minutes at 230 degreeC using the hot air dryer, and the black matrix which concerns on Examples 1-6 and Comparative Examples 1-4 was obtained.

  Table 3 shows the results of evaluation of developability, development margin, and the like for the black matrices of Examples 1 to 6 and Comparative Examples 1 to 4 obtained above. These evaluation methods were performed as follows.

Film thickness:
Measurement was performed using a stylus type step shape measuring device (trade name P-10, manufactured by KLA-Tencor Corp.).

Development time:
During alkali development, the time required to see all the patterns was recorded. If the pattern could not be seen even if the development time exceeded 120 seconds, it was marked as x.

Fine wire adhesion margin:
When the exposed portion was developed with a 10 μm pattern mask, the time during which the pattern portion maintained 10 ± 1 μm after the pattern was seen was recorded. The line width of the pattern part was measured using a length measuring microscope (trade name XD-20 manufactured by Nikon Corporation).

Taper shape:
Observe the developed pattern using a scanning electron microscope (trade name VE-780, manufactured by KEYENCE). If the cross-sectional shape of the pattern maintains a forward taper, ○, reverse taper and peeling occur. When it was, it was set as x.

Line shape:
With respect to the 10 μm line after development, the linearity of the pattern portion and the presence / absence of fringe were evaluated with the above measuring microscope. Therefore, the case where the linearity was good and the fringe was not generated was evaluated as ○ <good>, and the case where the fringe was generated and the linearity was poor was evaluated as x <defect>. Each item was evaluated as ◎ only when it was very good.

Optical density:
It measured using the optical densitometer (made by Otsuka Electronics Co., Ltd.).

  As is clear from the results of Table 3 above, the black matrices according to Examples 1 to 6 are excellent in each performance. In particular, the black matrices of Examples 4 to 6 are compared with those of Comparative Examples 3 and 4. It is excellent in developability and adhesiveness, and a fine line pattern can be formed even when the amount of photopolymerization initiator used is reduced. That is, the cured portion has a large difference in solubility in the alkaline developer between the cured portion and the uncured portion after irradiation with ultraviolet light or electron beam, and has good developability and high adhesion by increasing the number of ethylenically unsaturated bond groups in one molecule. It has been found that a membrane can be provided.

  The photosensitive resin composition for black matrix of the present invention has a higher solubility in an alkali developer than the conventional one and a high number of ethylenically unsaturated bond groups in one molecule, so that the crosslinking density after curing is high. . That is, since the difference in solubility in the alkaline developer between the cured portion and the uncured portion after irradiation with ultraviolet rays or electron beams is increased, a fine pattern can be formed even in a thin film or at a high colorant concentration. Therefore, it can be suitably used for various multicolor display bodies such as a color liquid crystal display device, a color facsimile, and an image sensor, and a color filter having a black matrix used for optical equipment and the like. The color filter thus obtained is extremely useful for, for example, a transmissive, reflective, or transflective color liquid crystal display device, a color imaging tube element, a color sensor, and the like.

Claims (3)

(I) an alkali-soluble resin represented by the following general formula (1) and having a carboxylic acid residue and a polymerizable unsaturated group in one molecule;

_{(Wherein, R 1, R 2, R} 3, and R ₄ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group. X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9 , 9-fluorenylene group or a direct bond, Y represents a tetravalent carboxylic acid residue, G represents a substituent having a polymerizable double bond and a carboxyl group, and Z is represented by the following general formula (2). And n represents a number of 1 to 20.)

(However, L represents a divalent or trivalent carboxylic acid residue, and p is 1 or 2.)
(Ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
A photosensitive resin composition for a black matrix comprising (iii) a photopolymerization initiator and (iv) a light-shielding pigment as essential components.   A cured product obtained by curing the photosensitive resin composition for a black matrix according to claim 1.   A color filter formed by a cured product obtained by applying and curing the photosensitive resin composition for a black matrix according to claim 1.