JP2013080207A - Photosensitive resin composition, and coating film and color filter using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in adhesion of a minute line pattern, and a coating film and a color filter formed using the same.SOLUTION: A photosensitive resin composition contains (A) alkali-soluble resin obtained by reacting a resin represented by the general formula (a-1) with a monofunctional epoxy compound, with an acid value in the range of 1-100 mgKOH/g; (B) photobase generator; (D) photopolymerizable monomer; and (E) photopolymerization initiator. In the formula, R-R, Y, Y, and P represent 9,9-fluorenyl group or the like, and X represents a carboxylic acid residue.

Description

  The present invention relates to a photosensitive resin composition, a coating film formed using the same, and a color filter.

  Color filters used for liquid crystal panels, image sensors, and the like are generally manufactured by a lithography method. In this lithography method, first, a black photosensitive resin composition is applied to a substrate, and then exposed and developed to form a black matrix. Next, for each photosensitive resin composition to which organic pigments of green, blue, and red are added, by repeating application, exposure, and development, a pattern of each color is formed at a predetermined position to manufacture a color filter.

  At this time, the photosensitive resin composition is required to be excellent in transparency, heat resistance, adhesion, and the like, and it is proposed to use a bisphenol type resin as a component. In particular, in Patent Document 1, by using an alkali-soluble resin obtained by further reacting a bisphenol-type resin with a monofunctional epoxy compound and having an acid value in the range of 1 to 100 mgKOH / g, high transparency, heat-resistant yellow In addition to modification, a photosensitive resin composition capable of forming a fine fine line has been reported.

JP 2006-284784 A

  In recent years, in order to ensure the reliability of products, there is a demand for high adhesion so as to adhere to a substrate even when a minute pattern is formed. The photosensitive resin composition proposed in Patent Document 1 is not satisfactory with respect to the adhesion of a fine line pattern.

  The present invention has been made in view of the above problems, and provides a photosensitive resin composition having excellent adhesion of a fine line pattern while using an alkali-soluble resin as proposed in Patent Document 1. With the goal. Moreover, the other objective is to provide the coating film and color filter which were formed using this photosensitive resin composition.

  As a result of intensive studies to achieve the above object, the present inventors can solve the above problems by using the resin proposed in Patent Document 1 and a specific compound as components of the photosensitive resin composition. As a result, the present invention has been completed.

（式中、Ｒ^ａ１、Ｒ^ａ２、Ｒ^ａ３、Ｒ^ａ４は、それぞれ独立に水素原子、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、Ｒ^ａ５は水素原子又はメチル基を示す。また、Ｐは−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、−Ｓｉ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、９，９−フルオレニル基又は単結合を示し、Ｘは４価のカルボン酸残基を示し、Ｙ^１、Ｙ^２はそれぞれ独立に水素原子又は−ＯＣ−Ｑ−（ＣＯＯＨ）_ｍを示し、Ｑはカルボン酸残基（ｍは１〜３の整数を示す）を示し、ｎは１〜２００の整数を示す。）

（式中、Ｒ^ｂ１及びＲ^ｂ２は、それぞれ独立に水素原子又は有機基を示す。ただし、Ｒ^ｂ１及びＲ^ｂ２の少なくとも一方は有機基を示す。Ｒ^ｂ１及びＲ^ｂ２は、それらが結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。Ｒ^ｂ３は、単結合又は有機基を示す。Ｒ^ｂ４及びＲ^ｂ５は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、又は有機基を示す。Ｒ^ｂ６、Ｒ^ｂ７、Ｒ^ｂ８、及びＲ^ｂ９は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基を示す。ただし、Ｒ^ｂ６及びＲ^ｂ７が水酸基となることはない。Ｒ^ｂ６、Ｒ^ｂ７、Ｒ^ｂ８、及びＲ^ｂ９は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。Ｒ^ｂ１０は、水素原子又は有機基を示す。） A first aspect of the present invention is an alkali-soluble resin (obtained by reacting a resin represented by the following formula (a-1) with a monofunctional epoxy compound and having an acid value in the range of 1 to 100 mgKOH / g. A), a photosensitive resin composition comprising a compound (B) represented by the following formula (b-1), a photopolymerizable monomer (D), and a photopolymerization initiator (E). It is a thing.

(In formula, R ^{<a1 >} , R ^{< a2 >} , R ^{< a3>} , R ^<a4> shows a hydrogen atom, a C1-C5 alkyl group, a halogen atom, or a phenyl group each independently, and R ^<a5> shows a hydrogen atom or a methyl group. P represents —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —Si (CH ₃ ) ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, 9,9-fluorenyl group or a single bond, X represents a tetravalent carboxylic acid residue, Y ¹ and Y ² each independently represents a hydrogen atom or —OC—Q— (COOH) _m , Q is A carboxylic acid residue (m represents an integer of 1 to 3), and n represents an integer of 1 to 200.)

^{(Wherein, R b1} and ^{R b2} each independently represent a hydrogen atom or an organic group. ^{However, .R b1} and ^{R b2} represents an organic group at least one of the ^{R b1} and ^{R b2} is to they are attached It may form a cyclic structure and may contain a heteroatom bond, R ^b3 represents a single bond or an organic group, R ^b4 and R ^b5 each independently represent a hydrogen atom, a halogen atom, or a hydroxyl group , mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, .R b6 showing a phosphonato group, or an organic ^radical, R ^b7 , ^Rb8 , and ^Rb9 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, or a nitro group. Nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, ammonio group, or organic group, provided that R ^b6 and R ^b7 are hydroxyl groups. no ^{.R b6, R b7, R b8} , and ^{R b9} are those two or more together, may form a cyclic structure, which may contain a binding heteroatom ^{.R b10} is Represents a hydrogen atom or an organic group.)

  The second aspect of the present invention is a coating film formed by curing the photosensitive resin composition according to the present invention, and the third aspect of the present invention is the application of the photosensitive resin composition according to the present invention. It is a color filter formed with a coating film obtained by curing.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition excellent in the adhesiveness of a micro line pattern can be obtained using the alkali-soluble resin proposed by patent document 1 by which transparency and heat-resistant yellowing are made favorable. . Therefore, the photosensitive resin composition of the present invention is particularly suitable for a photosensitive resin composition for color filters, and is suitably used for various multicolor displays such as a color liquid crystal display device, a display, a color facsimile, and an image sensor. be able to.

≪Photosensitive resin composition≫
The photosensitive resin composition according to the present invention includes an alkali-soluble resin (A), a compound (B), a photopolymerizable monomer (D), and a photopolymerization initiator (E) as essential components. And has properties as an alkali development type photosensitive resin composition. Other preferred optional components include the following components (F) and (G).
(F) Colorant (G) Epoxy compound having one or more epoxy groups

<Alkali-soluble resin (A)>
The alkali-soluble resin (A), which is an essential component of the photosensitive resin composition according to the present invention, is obtained by reacting a resin represented by the following formula (a-1) with a monofunctional epoxy compound, and has an acid value. Is a resin in the range of 1 to 100 mg KOH / g. When the acid value exceeds 100 mgKOH / g, the alkali solubility is too high, the pattern of the exposed portion penetrates into the alkaline aqueous solution, and the pattern portion is liable to form a chip or fringe shape, which is not preferable.

In the formula (a-1), R ^a1 , R ^a2 , R ^a3 and R ^a4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ^a5 represents a hydrogen atom. Or a methyl group is shown. P represents —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —Si (CH ₃ ) ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, 9 , 9-fluorenyl group or a single bond, X represents a tetravalent carboxylic acid residue, Y ¹ and Y ² each independently represent a hydrogen atom or —OC—Q— (COOH) _m , and Q represents a carbon An acid residue (m represents an integer of 1 to 3) is shown, and n is an integer of 1 to 200.

  Here, the resin represented by the above formula (a-1) is obtained by reacting (meth) acrylic acid with an epoxy compound having two glycidyl ether groups derived from bisphenols, and converting the resulting hydroxy group. It is an epoxy (meth) acrylate acid adduct obtained by further reacting a compound having a polycarboxylic acid with the compound. Since this resin has an unsaturated group derived from (meth) acrylic acid having a photopolymerizable unsaturated bond, it has polymerizability, and has an acidic group derived from a polyvalent carboxylic acid, and therefore exhibits alkali solubility. In the present specification, the acid component means polyvalent carboxylic acids, and (meth) acrylic acid means acrylic acid, methacrylic acid or both.

The resin represented by the above formula (a-1) is preferably derived from an epoxy compound represented by the following formula (a-2) and (meth) acrylic acid represented by the following formula (a-3). The This epoxy compound is derived from bisphenols.

In the above formula (a-2), R ^a1 , R ^a2 , R ^a3 , R ^a4 and P are the same as those in the above formula (a-1), but preferably R ^a1 , R ^a2 , R ^a3 and R ^a4. Is a hydrogen atom, preferably P is a 9,9-fluorenyl group. l is an integer of 0 to 10, preferably 0 or in the range of 0 to 2 as an average value. Here, the 9,9-fluorenyl group refers to a group represented by the following formula (a-4).

In the formula (a-3), R ^a5 is the same as R ^{a5 in the} formula (a-1).

  The epoxy compound represented by the above formula (a-2) is derived from bisphenols. Examples of bisphenols that give the above formula (a-2) include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, and 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, bi (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-hydroxydichlorophenyl) 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-dimethyl) Phenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, etc. That. 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 and the like are also preferable. Can be mentioned. Furthermore, 4,4'-biphenol, 3,3'-biphenol and the like are also preferred.

  The resin represented by the above formula (a-1) can be obtained via an epoxy compound derived from bisphenols as described above. In addition to such an epoxy compound, a phenol novolac type epoxy compound or cresol A novolak-type epoxy compound or the like can be used as long as it contains a compound having two glycidyl ether groups significantly. In addition, when bisphenols are converted to glycidyl ether, oligomer units are mixed. If the average value of l in the formula (a-2) is in the range of 0 to 10, preferably 0 to 2, the photosensitivity is increased. There is no problem in the performance of the conductive resin composition.

Such a reaction between the epoxy compound and (meth) acrylic acid may be carried out using about 2 mol of (meth) acrylic acid per 1 mol of the epoxy compound. The reaction product obtained by this reaction is an epoxy (meth) acrylate compound represented by the following formula (a-5).

In the above formula (a-5), R ^a1 , R ^a2 , R ^a3 , R ^a4 , R ^a5 , and P are the same as in the above formula (a-1).

  The reaction product obtained by the reaction of the epoxy compound and (meth) acrylic acid is reacted with the acid component to obtain a resin represented by the above formula (a-1). As the acid component, a polyvalent carboxylic acid capable of reacting with a hydroxy group in the molecule of the epoxy (meth) acrylate compound or an acid anhydride thereof (referred to as carboxylic acids) is used. Preferably, dicarboxylic acids and tetracarboxylic acids are used. Used together.

Here, as the dicarboxylic acid, a chain hydrocarbon dicarboxylic acid or its acid anhydride, an alicyclic dicarboxylic acid or its acid anhydride, an aromatic dicarboxylic acid or its acid anhydride is used.
Examples of the chain hydrocarbon dicarboxylic acid or its acid anhydride include succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citralmalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid. There are compounds such as acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid and the like, and further dicarboxylic acids having an arbitrary substituent introduced therein or acid anhydrides thereof may be used.
Examples of the alicyclic dicarboxylic acid or its acid anhydride include compounds such as hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, and any substituents introduced. Dicarboxylic acids or acid anhydrides thereof may be used.
Furthermore, examples of the aromatic dicarboxylic acid and its acid anhydride include compounds such as phthalic acid and isophthalic acid, and further dicarboxylic acids into which an arbitrary substituent is introduced or acid anhydrides thereof may be used.

The tetracarboxylic acids include chain hydrocarbon tetracarboxylic acid or its acid dianhydride, alicyclic tetracarboxylic acid or its acid dianhydride, or aromatic polyvalent carboxylic acid or its acid dianhydride. used.
Here, examples of the chain tetracarboxylic acid or acid anhydride thereof include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and the like, and further, tetracarboxylic acids having an introduced substituent or acid thereof. An anhydride may be used. Examples of the alicyclic tetracarboxylic acid or its acid anhydride include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid norbornanetetracarboxylic acid, and further substitution. It may be a tetracarboxylic acid having an introduced group or an acid anhydride thereof.
Furthermore, examples of the aromatic tetracarboxylic acid and its acid anhydride include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and acid anhydrides thereof, and further, The introduced tetracarboxylic acids or acid anhydrides thereof may be used.

  One or more dicarboxylic acids and tetracarboxylic acids can be used, respectively, and the use ratio of the dicarboxylic acids and tetracarboxylic acids is preferably in the range of 0.1 to 10 as the molar ratio of dicarboxylic acid / tetracarboxylic acid, preferably Is a range of 0.2 to 1.0. As for this use ratio, a ratio suitable for the effect of optimum molecular weight, alkali developability, light transmittance, heat resistance, solvent resistance, and pattern shape can be selected. Tend to be large and have a high molecular weight.

  A method for producing a resin represented by the above formula (a-1) by reacting the above formula (a-5), which is a reaction product obtained by a reaction between an epoxy compound and (meth) acrylic acid, with a carboxylic acid. The method is not particularly limited, and a known method as described in Patent Document 1 can be adopted. Advantageously, it is desirable to react quantitatively so that the acid component is 1/2 mole per mole of hydroxy group in the epoxy (meth) acrylate compound molecule. Moreover, as reaction temperature, it is 90-130 degreeC, Preferably it is 95-125 degreeC.

An example of a method for producing the resin represented by the above formula (a-1) is as follows when 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 above formula (a-2), and this bisphenolfluorene type epoxy compound. And a (meth) acrylic acid represented by the above formula (a-3) to synthesize a bisphenolfluorene type epoxy acrylate resin represented by the above formula (a-5), and then in a propylene glycol monomethyl solvent The bisphenol fluorene type epoxy acrylate resin and the acid component are reacted under heating to obtain a fluorene type resin represented by the formula (a-1).

  The resin represented by the above formula (a-1) obtained as described above is reacted with a monofunctional epoxy compound to become an alkali-soluble resin (A) having an acid value in the range of 1 to 100 mgKOH / g. . What is necessary is just to make reaction of alkali-soluble resin and a monofunctional epoxy compound react at 60-80 degreeC for 6 hours or more.

Here, the monofunctional epoxy resin used in the reaction is not particularly limited as long as it is a monofunctional epoxy resin. For example, it is a powder compound at room temperature such as epoxypropylphthalimide and epoxynorbornene, or phenylglycidyl. Examples thereof include high boiling point compounds such as ether and p-butylphenol glycidyl ether at room temperature. Among the monofunctional epoxy resins, those represented by the following formula (c-1) are preferable, and styrene oxide, glycidol and the like are exemplified as preferable ones. In the following formula (c-1), Z is _-C r _H 2r + 1, shows a _-C 6 _{H 5} or _-C s _H 2s -OH, r and s are each an integer of 1 to 10.

  The reaction between the resin represented by the above formula (a-1) and the monofunctional epoxy compound represented by the above formula (c-1) is such that the acid value of the alkali-soluble resin (A) obtained by reacting is the resin. The monofunctional epoxy compound is preferably reacted so that the acid value of (a-1) is 1/10 to 9/10, preferably 2/10 to 8/10.

  The mass average molecular weight of the alkali-soluble resin (A) is preferably 1000 to 40000, and more preferably 2000 to 30000. By setting it as the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.

  It is preferable that alkali-soluble resin (A) is 5-80 mass% with respect to solid content of the photosensitive resin composition, and it is more preferable that it is 15-50 mass%. By setting it as the above range, there is a tendency that developability is easily balanced.

<Compound (B)>
Another essential component of the photosensitive resin composition according to the present invention is a compound (B) represented by the following formula (b-1). This compound has good solubility in an organic solvent, and also generates a base upon irradiation or heating, and thus functions as a base generator. For this reason, when it is made to contain in the photosensitive resin composition, there exists an effect which improves the adhesiveness to a board | substrate, and it is possible to make the adhesiveness of a micro line pattern favorable.

In the above formula (b-1), R ^b1 and R ^b2 each independently represent a hydrogen atom or an organic group, but at least one of R ^b1 and R ^b2 represents an organic group.
^Examples of the organic group for R ^b1 and R ^b2 include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. This organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.
This organic group is usually monovalent, but can be a divalent or higher organic group when a cyclic structure is formed.

R ^b1 and R ^b2 may be bonded to each other to form a cyclic structure, and may further include a hetero atom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a condensed ring.

The bond other than the hydrocarbon group in the organic group of R ^b1 and R ^b2 is not particularly limited as long as the effect of the present invention is not impaired, and includes a bond containing a hetero atom such as an oxygen atom, a nitrogen atom, or a silicon atom. It is done. Specific examples include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (—N═C (—R) —, —C (═NR) —: R is A hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and the like.

From the viewpoint of heat resistance, the bonds other than the hydrocarbon group in the organic groups of R ^b1 and R ^b2 include ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, urethane bond, imino bond ( -N = C (-R)-, -C (= NR)-: R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, or a sulfinyl bond.

The substituent other than the hydrocarbon group in the organic group of R ^b1 and R ^b2 is not particularly limited as long as the effect of the present invention is not impaired, and is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group. , Cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy Group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxyimino group, alkyl ether group, alkenyl ether group, alkyl thioether group, alkenyl thioether group, aryl ether group, arylthio group Ether group, an amino group _{(-NH 2, -NHR, -NRR '} : R and R' each independently represent a hydrocarbon group). The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

Substituents other than hydrocarbon groups in the organic groups of R ^b1 and R ^b2 include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyano groups, cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanato groups, silyl groups. Group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, A phosphinyl group, a phosphono group, a phosphonato group, a hydroxyimino group, an alkyl ether group, an alkenyl ether group, an alkyl thioether group, an alkenyl thioether group, an aryl ether group, and an aryl thioether group are preferred.

Among these, as R ^b1 and R ^b2 , at least one of them is an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms, or a heterocycloalkyl group having 2 to 20 carbon atoms bonded to each other. Alternatively, it preferably forms a heteroaryl group. Examples of the heterocycloalkyl group include a piperidino group and a morpholino group, and examples of the heteroaryl group include an imidazolyl group and a pyrazolyl group.

In the formula (b-1), R ^b3 represents a single bond or an organic group.
^Examples of the organic group for R ^b3 include groups in which one hydrogen atom has been removed from an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, and the like. This organic group may contain a substituent in the organic group. Examples of the substituent include those exemplified for R ^b1 and R ^b2 . Further, this organic group may be either linear or branched.

Among these, R ^b3 is preferably a single bond, or a group in which one hydrogen atom is removed from an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms.

In the formula (b-1), R ^b4 and R ^b5 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, or a sulfo group. , Sulfonate groups, phosphino groups, phosphinyl groups, phosphono groups, phosphonate groups, or organic groups.
Examples of the organic group for R ^b4 and R ^b5 include those exemplified for R ^b1 and R ^b2 . As in the case of R ^b1 and R ^b2 , this organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

Among these, as R ^b4 and R ^b5 , each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, or 7 carbon atoms. -16 aryloxyalkyl group, C7-20 aralkyl group, C2-C11 alkyl group having a cyano group, C1-C10 alkyl group having a hydroxyl group, C1-C10 alkoxy group , An amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms (-COOR, -OCOR: R represents a hydrocarbon group. ), An aryl group having 6 to 20 carbon atoms, an electron donating group and / or an electron withdrawing group substituted with an aryl group having 6 to 20 carbon atoms, an electron donating group and / or an electron withdrawing group substituted benzyl group A cyano group is preferably a methylthio group. More preferably, both R ^b4 and R ^b5 are hydrogen atoms, or R ^b4 is a methyl group and R ^b5 is a hydrogen atom.

In the above formula (b-1), R ^b6 , R ^b7 , R ^b8 and R ^b9 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso A group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group.
Examples of the organic group for R ^b6 , R ^b7 , R ^b8 , and R ^b9 include those exemplified for R ^b1 and R ^b2 . As in the case of R ^b1 and R ^b2 , this organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

In the formula (b-1), R ^b6 and R ^b7 do not become a hydroxyl group. This is because when R ^b6 or R ^b7 is a hydroxyl group, a cyclization reaction occurs due to irradiation and heating, and energy is consumed for this purpose, so that sufficient adhesion of a fine line pattern cannot be obtained.

Two or more of R ^b6 , R ^b7 , R ^b8 , and R ^b9 may be bonded to form a cyclic structure, and may include a hetero atom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a condensed ring. For example, R ^b6 , R ^b7 , R ^b8 , and R ^b9 share two or more of them and share the atom of the benzene ring to which R ^b6 , R ^b7 , R ^b8 , and R ^b9 are bonded. A condensed ring such as naphthalene, anthracene, phenanthrene, and indene may be formed.

Among these, as R ^b6 , R ^b7 , R ^b8 , and R ^b9 , each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, or a group having 4 to 13 carbon atoms. A cycloalkenyl group, an aryloxyalkyl group having 7 to 16 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, carbon C1-C10 alkoxy group, C2-C11 amide group, C1-C10 alkylthio group, C1-C10 acyl group, C2-C11 ester group, C6-C20 Aryl group, electron donating group and / or electron withdrawing group substituted aryl group having 6 to 20 carbon atoms, electron donating group and / or electron withdrawing group substituted benzyl group, cyano group, methylthio group, A tro group is preferred.

In addition, as R ^b6 , R ^b7 , R ^b8 , and R ^b9 , two or more of them are bonded to each other and share a benzene ring atom to which R ^b6 , R ^b7 , R ^b8 , and R ^b9 are bonded. In the case where condensed rings such as naphthalene, anthracene, phenanthrene, and indene are formed, it is preferable from the viewpoint that the absorption wavelength becomes longer.
More preferably, all of R ^b6 , R ^b7 , R ^b8 , and R ^b9 are hydrogen atoms, or any one of R ^b6 , R ^b7 , R ^b8 , and R ^b9 is a nitro group, and the remaining 3 One is a hydrogen atom.

In the above formula (b-1), R ^b10 represents a hydrogen atom or an organic group.
As the organic group for R ^b10 , those exemplified for R ^b1 and R ^b2 can be mentioned. As in the case of R ^b1 and R ^b2 , this organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.
Since the compound (B) represented by the above formula (b-1) has an —OR ^b10 group at the para-position of the benzene ring, the solubility in an organic solvent is good.

Among the above, R ^b10 is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group.

  Among the compounds (B) represented by the above formula (b-1), particularly preferred specific examples include compounds represented by the following formulas.

  The compound (B) represented by the above formula (b-1) can be synthesized as in Examples described later.

  The content of the compound (B) is preferably 3 to 200 parts by mass and more preferably 50 to 100 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (E) described later. By setting it as said range, the adhesiveness of a micro line pattern can be made favorable, obtaining favorable developability.

<Photopolymerizable monomer (D)>
Another essential component of the photosensitive resin composition according to the present invention is a photopolymerizable monomer (D). Photopolymerizable monomers include monofunctional monomers and polyfunctional monomers.

  Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl ( And (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers can be used alone or in combination of two or more.

  On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meta Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydi Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (Meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene Examples thereof include polyfunctional monomers such as ethers, polyhydric alcohols and N-methylol (meth) acrylamide condensates, and triacryl formal. These polyfunctional monomers can be used alone or in combination of two or more.

  The content of the photopolymerizable monomer (D) is preferably 1 to 30% by mass and more preferably 5 to 20% by mass with respect to the solid content of the photosensitive resin composition. By setting it as the above range, it tends to be easy to balance sensitivity, developability, and resolution.

  The blending ratio of the alkali-soluble resin (A) and the photopolymerizable monomer (D) is 20/80 to 90/10, preferably 20/80 to 80/20 in mass ratio (A) / (D). More preferably, it is 40 / 60-80 / 20. When (A) / (D) is low, the cured product after photocuring becomes brittle, and since the acid value of the coating film is low in the unexposed area, the solubility in an alkali developer is lowered, and the pattern edge is Problems such as not being sharp and sharp are likely to occur. When (A) / (D) is high, the proportion of the photoreactive functional group in the resin is small and the formation of a crosslinked structure is not sufficient, and the acid value in the resin component is too high, so that the alkali development in the exposed area. Since the solubility in the liquid becomes high, there is a possibility that the formed pattern becomes thinner than the target line width or the pattern is likely to be lost.

<Photopolymerization initiator (E)>
Another essential component of the photosensitive resin composition according to the present invention is a photopolymerization initiator (E). It does not specifically limit as a photoinitiator, A conventionally well-known photoinitiator can be used.

  Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl- 4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4 -Dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone , 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone , Octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidar, 2-mercaptobenzoxazole, 2-mercapto Benzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophe ) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4′-bisdimethylaminobenzophenone (ie, Michler's ketone), 4,4′-bisdiethylaminobenzophenone (ie, ethyl Michler's) Ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether , Benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert- Butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenyl Acridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9- Cridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5 -Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl)- s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl ] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Toxistyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl -6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis- And trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, and the like. It is done. Among these, it is particularly preferable in terms of sensitivity to use an oxime-based photopolymerization initiator. These photopolymerization initiators can be used alone or in combination of two or more.

  It is preferable that content of a photoinitiator (E) is 0.5-20 mass parts with respect to 100 mass parts of solid content of the photosensitive resin composition. By setting it as said range, sufficient heat resistance and chemical-resistance can be acquired, a coating-film formation ability can be improved, and hardening failure can be suppressed.

<Colorant (F)>
The photosensitive resin composition according to the present invention may contain a colorant (F). By containing a colorant, for example, it is preferably used as a color filter forming application for a liquid crystal display. Moreover, by including a light-shielding agent as a colorant, for example, it is preferably used as a black matrix forming application in a color filter.

  Although it does not specifically limit as a coloring agent, For example, the compound classified into the pigment (Pigment) in the color index (CI; issue | issued by The Society of Dyers and Colorists), specifically, as follows It is preferable to use a color index (CI) number.

C. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same, and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180 185;
C. I. Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46 49, 51, 55, 59, 61, 63, 64, 71, 73;
C. I. Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same, and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;
C. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same, and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49 : 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64 : 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155 166, 168, 170, 171, 172, 174, 175, 176, 177, 78, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;
C. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same, and only the number is described) 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 66;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37;
C. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigment brown 28;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

  Moreover, when using a colorant as a light shielding agent, it is preferable to use a black pigment as the light shielding agent. Black pigments include carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, composite oxides, metal sulfides, metal sulfates, metal carbonates, etc. Various pigments can be mentioned regardless of organic matter and inorganic matter. Among these, it is preferable to use carbon black having high light shielding properties.

  As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used, but it is preferable to use channel black having excellent light shielding properties. Resin-coated carbon black may also be used.

  Resin-coated carbon black has lower electrical conductivity than carbon black without resin coating, so when used as a black matrix for liquid crystal display, it produces less current leakage and produces a highly reliable display with low power consumption. it can.

  Moreover, in order to adjust the color tone of carbon black, you may add said organic pigment suitably as an auxiliary pigment.

  Moreover, in order to disperse | distribute a coloring agent uniformly in the photosensitive resin composition, you may use a dispersing agent further. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

  In addition, the inorganic pigment and the organic pigment may be used alone or in combination, but when used in combination, the organic pigment is added in an amount of 10 to 10 parts by mass with respect to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. It is preferably used in the range of 80 parts by mass, and more preferably in the range of 20 to 40 parts by mass.

The content of the colorant (F) may be appropriately determined according to the use of the photosensitive resin composition, but as an example, it is 5 to 70 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive resin composition. Is preferable, and 25-60 mass parts is more preferable.
In particular, when forming a black matrix using a photosensitive resin composition, the amount of the light-shielding agent in the photosensitive resin composition is adjusted so that the OD value per 1 μm film thickness of the black matrix is 4 or more. It is preferable to do. If the OD value per film thickness of 1 μm in the black matrix is 4 or more, a sufficient display contrast can be obtained when used in a black matrix of a liquid crystal display.

<Epoxy compound (G) having one or more epoxy groups>
The photosensitive resin composition according to the present invention may contain an epoxy compound (G) having one or more epoxy groups. An epoxy resin can be mixed with the epoxy compound for the purpose of further improving adhesion and alkali resistance.

  Examples of the compound having an epoxy group include a phenol novolac epoxy resin, a cresol novolac epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a biphenyl epoxy resin, and an alicyclic epoxy resin. And compounds having at least one epoxy group such as glycidyl ether, phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether and glycidyl methacrylate.

  1-30 mass parts is preferable with respect to 100 mass parts of solid content of the photosensitive resin composition, and, as for content of this epoxy compound (G), 5-20 mass parts is more preferable.

  When the photosensitive resin composition according to the present invention is used for a color filter or the like, it is preferable to use an organic solvent in addition to the above components.

  Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether. , Diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, di Propylene glycol monomethyl ether, zip (Poly) alkylene glycol monoalkyl ethers such as pyrene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene (Poly) alkylene glycol monoalkyl ether acetates such as glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl Other ethers such as ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Lactic acid alkyl esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyacetic acid Ethyl, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-acetate -Propyl, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, pyruvate Other esters such as ethyl, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, N-dimethylformamide And amides such as N, N-dimethylacetamide. These organic solvents can be used alone or in combination of two or more.

  Among the above organic solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, and 3-methoxybutyl acetate are alkali-soluble. While exhibiting excellent solubility for the resin (A), the photopolymerizable monomer (D), the photopolymerization initiator (E), and the compound (B) represented by the formula (b-1), Since the dispersibility of the colorant (F) can be improved, it is preferable to use propylene glycol monomethyl ether acetate or 3-methoxybutyl acetate.

  The content of the organic solvent is preferably such that the solid content concentration of the photosensitive resin composition is 1 to 50% by mass, and more preferably 5 to 30% by mass.

  The photosensitive resin composition according to the present invention may contain various additives as necessary. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, and a surfactant.

  Such a photosensitive resin composition is prepared by mixing each component described above with a stirrer. In addition, you may filter using a membrane filter etc. so that the prepared photosensitive resin composition may become uniform.

≪Coating film≫
The coating film according to the present invention is obtained, for example, by applying a solution of the photosensitive resin composition to a substrate or the like, drying, irradiating light (including ultraviolet rays, radiation, etc.), and curing it. . 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.

≪Color filter≫
Next, the manufacturing method of the color filter using the photosensitive resin composition is demonstrated. First, on the surface of the substrate, if necessary, a light shielding layer is formed so as to partition a portion for forming pixels, and a liquid composition of a photosensitive resin composition in which, for example, a red pigment is dispersed on the substrate. After applying the product, pre-baking is performed to evaporate the solvent and form a coating film. Next, after exposing the coating film through a photomask, development using an alkaline developer is performed to dissolve and remove the unexposed portion of the coating film, and then post-baking to form a predetermined red pixel pattern. A pixel array arranged in an array is formed. Thereafter, using the liquid composition of the photosensitive resin composition in which the green or blue pigment is dispersed, the liquid composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above. By sequentially forming the pixel array and the blue pixel array on the same substrate, the pixel arrays of the three primary colors of red, green and blue are arranged on the substrate, and further, a protective film is formed on the photosensitive resin composition as a protective film thereon. In the same manner as described above, the liquid composition is coated, pre-baked, exposed, developed and post-baked to obtain a color filter on which a protective film is formed.

  When applying the liquid composition of 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 as well as a known solution dipping method and spray method is adopted. can do. 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 or the like, vacuum drying, or a combination thereof. The heating temperature and heating time in the pre-baking are appropriately selected according to the solvent to be used, and are performed, for example, at 80 to 120 ° C. for 1 to 10 minutes.

As the radiation used when producing the color filter, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 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 preferable to develop at 2 to 30 ° C. using a weakly alkaline aqueous solution containing 0.05 to 10% by mass of carbonate such as lithium carbonate, and to obtain 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 developing in this way, heat treatment (post-baking) is performed under the conditions of 180 to 250 ° C. and 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-baking. The patterned coating film of this invention is formed through each process by the above photolithography method.

  As a substrate used when forming a color filter having pixels and / or a black matrix, for example, glass, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyethersulfone, etc.), transparent such as ITO, gold, etc. A material in which an electrode is deposited or patterned is used. In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.

<Synthesis of alkali-soluble resin (A)>
An alkali-soluble resin (A) having an acid value in the range of 1 to 100 mgKOH / g obtained by reacting the resin represented by the formula (a-1) with a monofunctional epoxy compound is described in Patent Document 1 above. Was synthesized according to the method described.

[Alkali-soluble resin (A-1)]
In a 500 mL four-necked flask with a reflux condenser, 198.53 g of a 50% propylene glycol monomethyl ether acetate solution of fluorene type epoxy acrylate ASF-400 (trade name: manufactured by Nippon Steel Chemical Co., Ltd.) and cyclohexanecarboxylic dianhydride 27.6 g, 8.13 g of succinic anhydride and 0.45 g of triphenylphosphine were charged, and the mixture was stirred at 120 to 125 ° C. for 1 hour while being heated, and further stirred at 75 to 80 ° C. for 6 hours. Thereafter, 8.6 g of styrene oxide was added, and the mixture was further stirred at 80 ° C. for 6 hours to synthesize an alkali-soluble resin solution (A-1). The obtained resin solution had a solid content of 55% by mass and an acid value (in terms of solid content) of 80 mgKOH / g.

[Alkali-soluble resin (A-2)]
In a 500 mL four-necked flask equipped with a reflux condenser, 198.53 g of a 50% propylene glycol monomethyl ether acetate solution of fluorene type epoxy acrylate ASF-400 (trade name: manufactured by Nippon Steel Chemical Co., Ltd.) and benzophenone tetracarboxylic dianhydride 16.1 g of the product, 8.13 g of succinic anhydride and 0.45 g of triphenylphosphine were charged, and the mixture was stirred at 120 to 125 ° C. for 1 hour while being further heated at 75 to 80 ° C. for 6 hours. Thereafter, 8.6 g of styrene oxide was added, and the mixture was further stirred at 80 ° C. for 6 hours to synthesize an alkali-soluble resin solution (A-2). The obtained resin solution had a solid content of 55% by mass and an acid value (in terms of solid content) of 80 mgKOH / g.

<Synthesis of Compound (B)>
As the compound represented by the formula (b-1), compounds 1 to 20 represented by the following formula were prepared. The synthesis method of these compounds 1-20 is shown below. Moreover, the comparison compounds 1-8 represented by a following formula were prepared for the comparison.

[Synthesis Method of Compound 1]
3- (4-Methoxyphenyl) acrylic acid chloride 5.90 g (30 mmol) was dissolved in 50 ml of dry ether, triethylamine 4.59 ml (equivalent ratio 1.1), diethylamine 2.41 ml (equivalent ratio 1.1). And stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 1 (4.65 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis Method of Compound 2]
3- (4-Methoxyphenyl) acrylic acid chloride 5.90 g (30 mmol) was dissolved in 50 ml of dry ether, and triethylamine 4.59 ml (equivalent ratio 1.1) and aniline 3.07 ml (equivalent ratio 1.1). And stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 2 (6.31 g, 25 mmol). The yield based on acrylic acid chloride was 83%.

[Synthesis Method of Compound 3]
3- (4-Methoxyphenyl) acrylic acid chloride 5.90 g (30 mmol) was dissolved in 50 ml of dry ether, and triethylamine 4.59 ml (equivalent ratio 1.1) and imidazole 2.25 ml (equivalent ratio 1.1). And stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 3 (3.41 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis Method of Compound 4]
3- (4-Methoxyphenyl) acrylic acid chloride 5.90 g (30 mmol) was dissolved in 50 ml of dry ether, triethylamine 4.59 ml (equivalent ratio 1.1), morpholine 2.25 ml (equivalent ratio 1.1). And stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 4 (3.41 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis Method of Compound 5]
7.25 g (30 mmol) of 3- (2-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, 2.25 ml (equivalent ratio) of imidazole. 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 5 (4.08 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis Method of Compound 6]
7.25 g (30 mmol) of 3- (3-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, 2.25 ml (equivalent ratio) of imidazole. 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 6 (4.08 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis Method of Compound 7]
7.67 g (30 mmol) of 2-methyl-3- (2-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, imidazole 2. 25 ml (equivalent ratio 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 7 (4.29 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis Method of Compound 8]
7.67 g (30 mmol) of 2-methyl-3- (3-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, imidazole 2. 25 ml (equivalent ratio 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 8 (3.41 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis Method of Compound 9]
7.25 g (30 mmol) of 3- (2-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, 2.41 ml (equivalent ratio) of diethylamine. 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 9 (5.55 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis Method of Compound 10]
7.25 g (30 mmol) of 3- (3-nitro-4-methoxyphenyl) acrylic chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, 2.41 ml (equivalent ratio) of diethylamine. 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 9 (5.55 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis Method of Compound 11]
7.67 g (30 mmol) of 2-methyl-3- (2-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, 4.59 ml of triethylamine (equivalent ratio 1.1), diethylamine 2. 41 ml (equivalent ratio 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 11 (5.83 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis Method of Compound 12]
2.67 g (30 mmol) of 2-methyl-3- (3-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, 4.59 ml of triethylamine (equivalent ratio 1.1), diethylamine 2. 41 ml (equivalent ratio 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 12 (5.83 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis Method of Compound 13]
7.25 g (30 mmol) of 3- (2-nitro-4-methoxyphenyl) acrylic chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, 2.81 ml (equivalent ratio) of piperidine. 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 13 (5.62 g, 23 mmol). The yield based on acrylic acid chloride was 77%.

[Synthesis Method of Compound 14]
7.25 g (30 mmol) of 3- (3-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, 2.81 ml (equivalent ratio) of piperidine. 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 14 (5.62 g, 23 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis Method of Compound 15]
7.67 g (30 mmol) of 2-methyl-3- (2-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, 4.59 ml (equivalent ratio 1.1) of triethylamine, and piperidine 2. 81 ml (equivalent ratio 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 15 (5.83 g, 23 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis Method of Compound 16]
7.67 g (30 mmol) of 2-methyl-3- (3-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, 4.59 ml (equivalent ratio 1.1) of triethylamine, and piperidine 2. 81 ml (equivalent ratio 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 16 (5.83 g, 23 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis Method of Compound 17]
Dissolve 5.90 g (30 mmol) of 3- (4-methoxyphenyl) acrylic acid chloride in 50 ml of dry ether, 4.59 ml of triethylamine (equivalent ratio 1.1), 2.81 ml of piperidine (equivalent ratio 1.1). And stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 17 (3.41 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis Method of Compound 18]
6.32 g (30 mmol) of 2-methyl-3- (4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, 2.25 ml (equivalent ratio) of imidazole. 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 18 (3.62 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis Method of Compound 19]
6.32 g (30 mmol) of 2-methyl-3- (4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, 2.41 ml (equivalent ratio) of diethylamine. 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 19 (4.93 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis Method of Compound 20]
6.32 g (30 mmol) of 2-methyl-3- (4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, 3.07 ml (equivalent ratio) of aniline. 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 20 (4.29 g, 25 mmol). The yield based on acrylic acid chloride was 83%.

<Preparation of photosensitive resin composition>
[Example 1]
The following components were added to a solvent of 3-methoxybutyl acetate (MA) / propylene glycol monomethyl ether acetate (PM) / cyclohexanone (AN) = 60/20/20 (mass ratio), and mixed with a stirrer for 2 hours. Thereafter, the mixture was filtered through a 5 μm membrane filter to prepare a photosensitive resin composition having a solid content concentration of 15% by mass.
・ Alkali-soluble resin (A)
Resin (A-1) (solid content 55%, solvent: PM) 310 parts by mass / photopolymerizable monomer (D)
Dipentaerythritol hexaacrylate (DPHA): 175 parts by mass / photopolymerization initiator (E)
"OXE-02" (trade name: manufactured by BASF) ... 100 parts by mass-Compound (B) represented by the above formula (b-1)
Compound 1 ... 100 parts by mass / Colorant (F)
Carbon dispersion “CF Black” (trade name: Mikuni Color Co., Ltd., solid content 25%, solvent: MA): 450 parts by mass / epoxy compound (G)
“Ogsol EG-200” (trade name: manufactured by Osaka Gas Chemical Co., Ltd.): 50 parts by mass

[Examples 2 to 20]
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compounds 2 to 20 were used in place of the compound 1, respectively.

[Examples 21 to 40]
A photosensitive resin composition was prepared in the same manner as in Examples 1 to 20, except that the resin (A-2) was used instead of the resin (A-1).

[Comparative Examples 1-8]
A photosensitive resin composition was prepared in the same manner as in Example 1 except that each of Comparative Compounds 1 to 8 was used instead of Compound 1.
[Comparative Examples 9 to 16]
A photosensitive resin composition was prepared in the same manner as in Comparative Examples 1 to 8, except that the resin (A-2) was used instead of the resin (A-1).

<Evaluation>
The photosensitive resin compositions of Examples 1 to 40 and Comparative Examples 1 to 16 were applied on a glass substrate (100 mm × 100 mm) using a spin coater, pre-baked at 90 ° C. for 120 seconds, and a film thickness of 1.0 μm. A coating film was formed. Next, using a mirror projection aligner (product name: TME-150 RTO, manufactured by Topcon Corporation), the exposure gap was set to 50 μm, and the coating film was irradiated with ultraviolet rays through a negative mask on which a 20 μm line pattern was formed. The exposure amount was set in four stages of ²⁰ , 40, 60, and 120 mJ / cm ² . The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26 ° C. for 40 seconds and then post-baked at 230 ° C. for 30 minutes to form a line pattern.
Similarly, the coating film was irradiated with ultraviolet rays at an exposure gap of 50 μm through a negative mask on which line patterns of 2, 5, 10, and 20 μm were formed. The exposure amount was 20 mJ / cm ² . The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26 ° C. for 40 seconds and then post-baked at 230 ° C. for 30 minutes to form a line pattern.

The formed line pattern was observed with an optical microscope, and pattern straightness was evaluated. The pattern straightness was evaluated as “good” when the edge of the line was not rattled, and “bad” when it was rattled.
Moreover, the line pattern was observed with the optical microscope, and pattern adhesiveness was evaluated. The pattern adhesion is "good" when the line pattern is formed without being peeled from the substrate, "bad" when the line pattern is formed but the pattern is missing, and the line pattern is formed by peeling from the substrate. What was not done was rated as “none”.
Furthermore, the presence or absence of a residue in the unexposed part after development was evaluated.
The results are shown in Tables 1 to 8 below.

As can be seen from Tables 1 and 2, when the photosensitive resin compositions of Examples 1 to 40 containing the compounds 1 to 20 represented by the formula (b-1) are used, it is 60 mJ / cm ^2. Even with a low exposure amount, a line pattern having excellent linearity could be formed. In particular, a photosensitive resin composition containing compounds 1, 3, 7, 9, 18, and 19 can form a line pattern with excellent linearity even at a very low exposure amount of 20 mJ / cm ^2. I was able to.

Further, as can be seen from Tables 3 and 4, even with a low exposure amount of 20 mJ / cm ² , the 10 μm line pattern was in close contact with the substrate, and there was no development residue. In particular, in the photosensitive resin composition containing the compounds 1, 3, 7, and 9, the adhesion was good even with a fine pattern of 2 μm.

On the other hand, the photosensitive resin composition containing the comparative compounds 1 to 8 could not form a line pattern excellent in linearity at an exposure amount of 60 mJ / cm ² or less. Further, at a low exposure amount of 20 mJ / cm ² , only a 20 μm line pattern was adhered to the substrate, and smaller line patterns were peeled off.

Claims (6)

An alkali-soluble resin (A) obtained by reacting a resin represented by the following formula (a-1) with a monofunctional epoxy compound and having an acid value in the range of 1 to 100 mgKOH / g; A photosensitive resin composition comprising the compound (B) represented by 1), a photopolymerizable monomer (D), and a photopolymerization initiator (E).

(In formula, R ^{<a1 >} , R ^{< a2 >} , R ^{< a3>} , R ^<a4> shows a hydrogen atom, a C1-C5 alkyl group, a halogen atom, or a phenyl group each independently, and R ^<a5> shows a hydrogen atom or a methyl group. P represents —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —Si (CH ₃ ) ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, 9,9-fluorenyl group or a single bond, X represents a tetravalent carboxylic acid residue, Y ¹ and Y ² each independently represents a hydrogen atom or —OC—Q— (COOH) _m , Q is A carboxylic acid residue (m represents an integer of 1 to 3), and n represents an integer of 1 to 200.)

^{(Wherein, R b1} and ^{R b2} each independently represent a hydrogen atom or an organic group. ^{However, .R b1} and ^{R b2} represents an organic group at least one of the ^{R b1} and ^{R b2} is to they are attached It may form a cyclic structure and may contain a heteroatom bond, R ^b3 represents a single bond or an organic group, R ^b4 and R ^b5 each independently represent a hydrogen atom, a halogen atom, or a hydroxyl group , mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, .R b6 showing a phosphonato group, or an organic ^radical, R ^b7 , ^Rb8 , and ^Rb9 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, or a nitro group. Nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, ammonio group, or organic group, provided that R ^b6 and R ^b7 are hydroxyl groups. no ^{.R b6, R b7, R b8} , and ^{R b9} are those two or more together, may form a cyclic structure, which may contain a binding heteroatom ^{.R b10} is Represents a hydrogen atom or an organic group.) The photosensitive resin composition according to claim 1, wherein the monofunctional epoxy compound is represented by the following general formula (c-1).

(Wherein, Z _is, -C _{r H} 2r + _1, shows a _-C 6 _{H 5} or _-C s _H 2s -OH, r and s are each an integer of 1 to 10.)   The photosensitive resin composition of Claim 1 or 2 which further contains a coloring agent (F).   The photosensitive resin composition according to any one of claims 1 to 3, further comprising an epoxy compound (G) having one or more epoxy groups.   A coating film formed by curing the photosensitive resin composition according to claim 1.   A color filter formed with a coating film obtained by applying and curing the photosensitive resin composition according to claim 1.