JP6037706B2 - Photosensitive resin composition, color filter, and liquid crystal display device - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a color filter and a liquid crystal display device formed using the photosensitive resin composition.

  A photosensitive resin composition comprising a resin, a photopolymerizable monomer, a photopolymerization initiator, etc. for forming color pixels, black matrix, overcoat, ribs, spacers, etc. of color filters used in liquid crystal panels such as liquid crystal displays ( Resist) is used.

Such a photosensitive resin composition is generally subjected to a photolithographic process that undergoes steps of coating, drying, exposure, and development.
(1) Residues and background stains do not occur in the removed part in the development process. (2) The removed part has sufficient solubility. (3) The pixel formability such as the sharpness of the pattern edge is always improved. Although it is required, when a pixel is formed using a photosensitive colored resin composition having a high colorant content,
(1) Residues and background stains occur on the substrate in the unexposed area in the development process. (2) The sharpness of the edge shape of the pixel is inferior because good solubility cannot be obtained in the unexposed area (3 ) The phenomenon that the sensitivity of the pixels formed in the exposed area is not sufficient and the surface smoothness is notable is likely to occur remarkably, which is a serious problem in practical use.

In particular, when a light blocking capability is required in the entire wavelength region of light, such as a resin black matrix,
(1) It is extremely difficult to make a difference in crosslink density between the exposed part and the unexposed part. (2) A difference in crosslink density in the film thickness direction occurs even in the exposed part. Even if it is sufficiently cured, it does not cure on the basal plane side. (3) Since a large amount of black color material that is insoluble in the developer is blended, there is a significant decrease in developability, etc. It was an obstacle.

  In order to solve such problems, Patent Document 1 proposes a photosensitive resin composition containing an alkali-soluble unsaturated resin having a specific structure as an organic binder.

JP 2006-79064 A

  By the way, in recent years, from the viewpoint of further improving productivity, the photosensitive resin composition is required to be able to form a pattern having a good shape even with a low exposure amount. Moreover, in order to ensure the reliability of a product, as a photosensitive resin composition, it is calculated | required to have high adhesiveness which closely_contact | adheres to a board | substrate, even when a micro pattern is formed.

  However, the photosensitive resin composition of Patent Document 1 still has insufficient characteristics to form a pattern with low exposure and excellent adhesion.

  The present invention has been made in view of the above problems, and a photosensitive resin composition capable of forming a pattern having excellent adhesion with a low exposure amount, and a color filter formed using the photosensitive resin composition An object of the present invention is to provide a liquid crystal display device.

  As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by using a specific compound in addition to the alkali-soluble unsaturated resin described in Patent Document 1, and to complete the present invention. It came.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子又は有機基を示す。ただし、Ｒ^１及びＲ^２の少なくとも一方は有機基を示す。Ｒ^１及びＲ^２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^３は、単結合又は有機基を示す。Ｒ^４及びＲ^５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^６、Ｒ^７、Ｒ^８、及びＲ^９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^６及びＲ^７が水酸基となることはない。Ｒ^６、Ｒ^７、Ｒ^８、及びＲ^９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^１０は、水素原子又は有機基を示す。） A first aspect of the present invention is a photosensitive resin composition containing an organic binder and a compound represented by the following formula (1), wherein the organic binder comprises at least two or more in the molecule. It contains an alkali-soluble unsaturated resin obtained by reacting a reaction product of an epoxy compound having an epoxy group (a) with an unsaturated group-containing carboxylic acid (b) with a compound having an isocyanate group (c). It is the photosensitive resin composition characterized by the above-mentioned.

(In the formula (1), ^{R 1} and ^{R 2} each independently represent a hydrogen atom or an organic group. However, .R ¹ and ^{R 2} represents an organic group at least one of the ^{R 1} and ^{R 2,} they R ³ may represent a single bond or an organic group, R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, or may be bonded to each other to form a cyclic structure. An 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, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group. ⁶ , R ⁷ , R ⁸ and R ⁹ 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 sulfur group. Indino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, ammonio group, or organic group, provided that R ⁶ and R ⁷ do not become a hydroxyl group. ⁶ , R ⁷ , R ⁸ , and R ⁹ may be bonded to each other to form a cyclic structure, and may include a heteroatom bond, R ¹⁰ may be a hydrogen atom or Indicates an organic group.)

  A second aspect of the present invention is a photosensitive resin composition containing an organic binder and a compound represented by the above formula (1), wherein the organic binder has at least two molecules in the molecule. An alkali-soluble unsaturated compound obtained by reacting a reaction product of a phenolic hydroxyl group-containing compound (f) having a phenolic hydroxyl group and an unsaturated group-containing epoxy compound (g) with a compound (c) having an isocyanate group. It is a photosensitive resin composition characterized by containing resin.

  The third aspect of the present invention is a color filter formed using the photosensitive resin composition in the first or second aspect.

  The 4th aspect of this invention is a liquid crystal display device which has the member formed using the photosensitive resin composition in a 1st or 2nd aspect.

  According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a pattern with low exposure and excellent adhesion, and a color filter and a liquid crystal display device formed using the photosensitive resin composition. it can.

≪Photosensitive resin composition≫
<Compound represented by Formula (1)>
The photosensitive resin composition according to the present invention contains a compound represented by the following formula (1). Below, the compound represented by Formula (1) is demonstrated first.

In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom or an organic group, but at least one of R ¹ and R ² represents an organic group.
Examples of the organic group in R ¹ and R ² 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 ¹ and R ² 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 ¹ and R ² 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 bond other than the hydrocarbon group in the organic group of R ¹ and R ² includes 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 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 ¹ and R ² 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, aryl thioether 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 ¹ and R ² 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 the above, as R ¹ and R ² , 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 above formula (1), R ³ represents a single bond or an organic group.
Examples of the organic group for R ³ include groups in which one hydrogen atom has been removed from an alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, aryl group, 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 ¹ and R ² . Further, this organic group may be either linear or branched.

Among these, R ³ 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 above formula (1), R ⁴ and R ⁵ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group. A group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group;
Examples of the organic group for R ⁴ and R ⁵ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , 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, R ⁴ and R ⁵ are each independently 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 , Amino group is preferably a methylthio group. More preferably, both R ⁴ and R ⁵ are hydrogen atoms, or R ⁴ is a methyl group and R ⁵ is a hydrogen atom.

In the above formula (1), R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, A sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group, or an organic group is shown.
Examples of the organic group for R ⁶ , R ⁷ , R ⁸ , and R ⁹ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , 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 above formula (1), R ⁶ and R ⁷ do not become a hydroxyl group. When R ⁶ or R ⁷ is a hydroxyl group, a cyclization reaction occurs due to electromagnetic wave irradiation and heating. For this reason, even if such a compound is contained in the photosensitive resin composition, light energy is consumed for cyclization, and good micropatterning characteristics cannot be obtained. On the other hand, the compound represented by the above formula (1) does not cause a cyclization reaction because R ⁶ and R ⁷ do not become a hydroxyl group, and is favorable when contained in the photosensitive resin composition. Micropatterning characteristics can be obtained.

Two or more of R ⁶ , R ⁷ , R ⁸ , and R ⁹ 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 6, R 7, R} 8, and ^{R 9} may combine two or more of ^{them, R 6, R 7, R} 8, and share an atom of the benzene ring ^{to which R 9} is attached A condensed ring such as naphthalene, anthracene, phenanthrene, and indene may be formed.

Among these, R ⁶ , R ⁷ , R ⁸ , and R ⁹ are each independently 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, nitro On the basis Preferably there is.
In addition, as R ⁶ , R ⁷ , R ⁸ , and R ⁹ , two or more of them are bonded to share a benzene ring atom to which R ⁶ , R ⁷ , R ⁸ , and R ⁹ 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 ⁶ , R ⁷ , R ⁸ , and R ⁹ are hydrogen atoms, or any one of R ⁶ , R ⁷ , R ⁸ , and R ⁹ is a nitro group, and the remaining 3 One is a hydrogen atom.

In the formula ^{(1), R 10} represents a hydrogen atom or an organic group.
Examples of the organic group for R ¹⁰ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , 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 represented by the above formula (1) has an —OR ¹⁰ group at the para-position of the benzene ring, the solubility in an organic solvent is good.

Among these, R ¹⁰ is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group.

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

Such a compound represented by the above formula (1) has good solubility in an organic solvent, and when it is contained in a photosensitive resin composition, it is possible to obtain good fine patterning characteristics.
In addition, this compound is compoundable like the Example mentioned later.

<Alkali-soluble unsaturated resin>
If the alkali-soluble unsaturated resin as the organic binder contained in the photosensitive resin composition of the present invention has the same chemical structure as the compound described in the claims of the present application, the present invention The production method is not particularly limited, and examples thereof include [A-1] and [A-2] below.

[A-1] A reaction product of an epoxy compound (a) having at least two epoxy groups in the molecule and an unsaturated group-containing carboxylic acid (b) is further reacted with a compound (c) having an isocyanate group. An alkali-soluble unsaturated resin obtained by making it. This alkali-soluble unsaturated resin is used for adjusting the acid value after adding the compound (c) having an isocyanate group to the hydroxyl group of the reaction product of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b). It is preferable to further add a polybasic acid anhydride (d). Moreover, after adding a polybasic acid anhydride (d) to the isocyanate compound (c) addition product of the reaction product of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b), further, the produced carboxyl What added the epoxy-group containing compound (e) to some groups may be used.
[A-2] A reaction product of a phenolic hydroxyl group-containing compound (f) having at least two phenolic hydroxyl groups in the molecule and an unsaturated group-containing epoxy compound (g), and a compound having an isocyanate group ( An alkali-soluble unsaturated resin obtained by reacting with c). This alkali-soluble unsaturated resin is obtained by adding an isocyanate group-containing compound (c) to the hydroxyl group of the reaction product of the phenolic hydroxyl group-containing compound (f) and the unsaturated group-containing epoxy compound (g), It is preferable that a polybasic acid anhydride (d) is further added for adjustment. Moreover, after adding polybasic acid anhydride (d) to the isocyanate compound (c) addition product of the reaction product of the phenolic hydroxyl group-containing compound (f) and the unsaturated group-containing epoxy compound (g), An epoxy group-containing compound (e) may be added to a part of the generated carboxyl group.

  The photosensitive resin composition of this invention should just contain at least 1 sort (s) of the alkali-soluble unsaturated resin of said [A-1] or [A-2] as an organic binder, [A-1 And two or more types of alkali-soluble unsaturated resins of [A-2], or one or more types of alkali-soluble unsaturated resins of [A-1] and [A-2. And one or more alkali-soluble unsaturated resins.

［式（Ｉ−ａ）中、Ｘは、下記式（ＩＩ）で表される。

（式（ＩＩ）中、Ｒ^１１〜Ｒ^２６は、それぞれ独立に、水素原子、炭素数１〜１２のアルキル基、又は置換基を有していてもよいフェニル基を示し、Ｒ^１１とＲ^１２、Ｒ^１３とＲ^１４がそれぞれ共にアルキル基の場合は互いに連結して環を形成していてもよい。ｎは０又は１である。）］ (Epoxy compound having at least two epoxy groups in the molecule (a))
The epoxy compound (a) is not particularly limited as long as it has at least two epoxy groups in the molecule, and examples thereof include an epoxy compound represented by the following general formula (Ia).

[In the formula (Ia), X is represented by the following formula (II).

(In formula (II), R ^{11 to} R ²⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group which may have a substituent, and R ¹¹ and R ^12. , When R ¹³ and R ¹⁴ are both alkyl groups, they may be linked to each other to form a ring. N is 0 or 1)]

  In the above general formula (Ia), if the molecular weight of the X site is too small, the solubility in an alkaline developer is too fast, and particularly in the resin black matrix, penetration of the developer occurs even in the exposed area, and adhesion Sex worsens. On the other hand, if the molecular weight of the X site is too large, the solubility in an alkali developer is too slow, so that productivity is deteriorated due to an extension of the tact time. The molecular weight of the X moiety is preferably 200 or more, more preferably 220 or more, still more preferably 280 or more, particularly preferably 300 or more, particularly preferably 330 or more, preferably 430 or less, more preferably 410 or less, still more preferably Is 380 or less. Below, it is an epoxy compound represented by the said general formula (Ia), Comprising: The epoxy compound of molecular weight 200-430 may be called "epoxy compound (a-1)."

In the general formula (Ia), the alkyl group of R ^{11 to} R ²⁶ may be any of a linear alkyl group, a branched alkyl group, and a cycloalkyl group, and the alkyl group is linear or branched. In this case, the preferred carbon number is 1 to 10, and in the case of a cycloalkyl group, the preferred carbon number is 5 to 10.

Examples of the ring formed by connecting R ¹¹ and R ¹² , R ¹³ and R ¹⁴ include a cycloalkane ring having 5 to 15 carbon atoms or an adamantane ring. In addition, the ring formed by connecting R ¹¹ and R ¹² , R ¹³ and R ¹⁴ may have an arbitrary number of substituents at an arbitrary position, and the substituent includes 1 to 1 carbon atoms. 5 alkyl groups.

（一般式（ＩＩＡ）〜（ＩＩＣ）において、Ｒ^１１〜Ｒ^２６及びｎは上記一般式（ＩＩ）におけると同義である。） X in the general formula (Ia) is preferably represented by the following general formula (IIA), (IIB) or (IIC).

(In the general formulas (IIA) to (IIC), R ^{11 to} R ²⁶ and n have the same meaning as in the general formula (II).)

（式中、Ｒ^１１，Ｒ^１２は前記一般式（ＩＩ）におけると同義である。） The general formula (IIA) is also preferably represented by the following general formula (IIAa) or (IIab).

(In the formula, R ¹¹ and R ¹² have the same meanings as in the general formula (II).)

  Specific examples of the X site that satisfy the above conditions include the following structures, but are not limited to the following.

（Ｒ^５１，Ｒ^５２はそれぞれ独立に、置換基を有していてもよいアルキレン基、又は置換基を有していてもよいアリーレン基を示し、ｊ，ｋはそれぞれ独立に０〜１０の整数を示す。）

(R ⁵¹ and R ⁵² each independently represents an alkylene group which may have a substituent, or an arylene group which may have a substituent, and j and k are each independently an integer of 0 to 10) Is shown.)

  Among the above exemplified structures, (X-1) to (X-12) and (X-40) to (X-43) are the same as those in the general formula (Ia) where X is the general formula (IIAa). Or, it is a specific example of what is represented by (IIAb), and among these, in particular, the structure represented by (X-1), (X-2), (X-40), and (X-41) Those are preferred.

（一般式（ＩＩＤ），（ＩＩＥ）において、Ｒ^１１，Ｒ^１２は上記一般式（ＩＩ）におけると同義であり、Ｒ^１７〜Ｒ^３４はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３のアルキル基を示す。） The epoxy compound (a) used in the present invention is an epoxy compound represented by the above general formula (Ia), and an X-molecular weight of X is less than 200 or more than 480 (hereinafter referred to as “epoxy compound (a-2)”) May be referred to as “.”, And such an epoxy compound (a-2) may be used in combination with the epoxy compound (a-1). Examples of the epoxy compound (a-2) include compounds in which, in the general formula (Ia), X is represented by the following general formula (IID) or (IIE).

(In General Formulas (IID) and (IIE), R ¹¹ and R ¹² have the same meanings as in General Formula (II) above, and R ^{17 to} R ³⁴ each independently have a hydrogen atom or a substituent. It represents an alkyl group having 1 to 3 carbon atoms.)

（一般式（ＩＩＤａ）において、Ｒ^１１，Ｒ^１２は上記一般式（ＩＩ）におけると同義であり、Ｒ^２７，Ｒ^３１はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３のアルキル基を示す。） Moreover, among the said epoxy compound (a-2), the compound by which X is represented with the following general formula (IIDa) is especially preferable.

(In General Formula (IIDa), R ¹¹ and R ¹² have the same meanings as in General Formula (II) above, and R ²⁷ and R ³¹ each independently represent a hydrogen atom or a carbon number that may have a substituent. 1 to 3 alkyl groups)

  When using the said epoxy compound (a-2) and an epoxy compound (a-1) together, an epoxy compound (a-2) is 20 mass% or less normally with respect to an epoxy compound (a-1), Preferably it is 15 It is preferable to use together by mass% or less.

The epoxy compound represented by the general formula (Ia) is, for example, a compound represented by the following general formula (IV) and an epihalohydrin such as epichlorohydrin or epibromohydrin, sodium hydroxide, potassium hydroxide, or the like. It can obtain by making it react at the temperature of 20-120 degreeC for 1 to 10 hours in presence of alkali metal hydroxide.
HO-X-OH (IV)
(In general formula (IV), X represents the same meaning as in general formula (Ia).)

  In the reaction for obtaining the epoxy compound represented by the general formula (Ia), an aqueous solution of the alkali metal hydroxide may be used. In that case, the aqueous solution of the alkali metal hydroxide is continuously reacted. A method may be employed in which water and epihalohydrin are continuously distilled under reduced pressure or normal pressure while being added to the system, followed by liquid separation, water removal, and epihalohydrin being continuously returned to the reaction system.

  Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added as a catalyst to a dissolved mixture of the compound represented by the general formula (IV) and epihalohydrin at 50 to 150 ° C. To the halohydrin etherified product of the compound represented by the general formula (IV) obtained by reacting for 1 to 5 hours, a solid or aqueous solution of an alkali metal hydroxide is added, and again at a temperature of 20 to 120 ° C., 1 to A method of reacting for 10 hours to dehydrohalogenate (ring closure) may be used.

  The amount of epihalohydrin used in such a reaction is usually 1 mol or more, preferably 2 mol or more, usually 30 mol or less, preferably 20 mol or less, based on 1 equivalent of the hydroxyl group of the compound represented by formula (IV). It is. The amount of the alkali metal hydroxide used is usually 0.8 mol or more, preferably 0.9 mol or more, usually 15 mol or less, preferably 1 mol per 1 equivalent of the hydroxyl group of the compound represented by formula (IV). 11 mol or less.

  Furthermore, in order to make the reaction proceed smoothly, the reaction may be carried out by adding an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide in addition to alcohols such as methanol and ethanol. When alcohols are used, the amount used is usually 2% by mass or more, preferably 4% by mass or more, and usually 20% by mass or less, preferably 15% by mass or less, based on the amount of epihalohydrin. Moreover, when using an aprotic polar solvent, the usage-amount is 5 mass% or more normally with respect to the quantity of epihalohydrin, Preferably it is 10 mass% or more, and is 100 mass% or less normally, Preferably it is 90 mass% or less.

  After the epoxidation reaction product is washed with water or without washing with water, epihalohydrin and other added solvents are removed at 110 to 250 ° C. under a pressure of 1.3 kPa (10 mmHg) under reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is dissolved. The reaction can be carried out by adding an aqueous solution to ensure ring closure. In this case, the amount of alkali metal hydroxide used is preferably 0.01 mol or more, particularly preferably 0.05 mol or more, based on 1 equivalent of the hydroxyl group of the compound represented by formula (IV) used for epoxidation. And preferably 0.3 mol or less, particularly preferably 0.2 mol or less. The reaction temperature is 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and further, the epoxy compound represented by the general formula (Ia) is removed by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure. Is obtained.

  The epoxy compound (a) used in the present invention is not limited to the epoxy compound represented by the general formula (Ia), and specific examples thereof include bisphenol A type epoxy resins (for example, oil-based shell epoxy ( "Epicoat 828", "Epicoat 1001", "Epicoat 1002", "Epicoat 1004", etc.), an epoxy resin obtained by reaction of an alcoholic hydroxyl group of bisphenol A type epoxy resin with epichlorohydrin (for example, Nippon Kayaku ( "NER-1302" (epoxy equivalent 323, softening point 76 ° C)), bisphenol F type resin (for example, "Epicoat 807", "EP-4001", "EP-4002" manufactured by Yuka Shell Epoxy Co., Ltd.) ”,“ EP-4004 etc. ”), alcoholic properties of bisphenol F type epoxy resin Epoxy resins obtained by the reaction of acid groups and epichlorohydrin (for example, “NER-7406” (epoxy equivalent 350, softening point 66 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, “YX-4000” manufactured by Yuka Shell Epoxy Co., Ltd.), phenol novolac type epoxy resin (for example, “EPPN-201” manufactured by Nippon Kayaku Co., Ltd., “EP-152” manufactured by Yuka Shell Epoxy Co., Ltd.) “EP-154”, “DEN-438” manufactured by Dow Chemical Co., Ltd.), cresol novolac type epoxy resin (for example, “EOCN-102S”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd.) "), Triglycidyl isocyanurate (for example," TEPIC "manufactured by Nissan Chemical Co., Ltd.), Methane type epoxy resin (for example, “EPPN-501”, “EPN-502”, “EPPN-503” manufactured by Nippon Kayaku Co., Ltd.), fluorene epoxy resin (for example, cardo epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) "ESF-300"), alicyclic epoxy resin ("Celoxide 2021P", "Celoxide EHPE" manufactured by Daicel Chemical Industries, Ltd.), dicyclopentadiene type epoxy obtained by glycidylation of phenol resin by reaction of dicyclopentadiene and phenol Resin, “XD-1000” manufactured by Nippon Kayaku Co., Ltd., “EXA-7200” manufactured by Dainippon Ink Co., Ltd., “NC-3000”, “NC-7300” manufactured by Nippon Kayaku Co., Ltd.), and the like.

  Another example of the epoxy compound (a) is a copolymerization type epoxy resin. Examples of the copolymerization type epoxy resin include glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, vinylcyclohexene oxide and the like (hereinafter referred to as “first component of copolymerization type epoxy resin”) and other monofunctional functions. Ethylenically unsaturated group-containing compound (hereinafter referred to as “second component of copolymerization type epoxy resin”), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl Acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α-methylstyrene, glycerin mono (meth) acrylate, the following general formula (IA) From the compound represented by Or a copolymer obtained by reacting with one or two or more types. (In this specification, “(meth) acrylate”, “(meth) acryl˜”, etc. are “acrylate or “Methacrylate”, “acrylic or methacrylic” or the like, for example, “(meth) acrylic acid” described later means “acrylic acid or methacrylic acid”).

（式中、Ｒ^３１は水素原子又はエチル基、Ｒ^３２は水素原子又は炭素数１〜６のアルキル基を示し、ｒは２〜１０の整数である。）

(In the formula, R ³¹ represents a hydrogen atom or an ethyl group, R ³² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and r is an integer of 2 to 10).

  Examples of the compound of the general formula (IA) include polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate and tetraethylene glycol mono (meth) acrylate, and methoxydiethylene glycol mono (meth) ) Acrylate, methoxytriethylene glycol mono (meth) acrylate, methoxytetraethylene glycol mono (meth) acrylate, and other alkoxy polyethylene glycol (meth) acrylates.

  As for the molecular weight of the said copolymerization type epoxy resin, about 1000-200000 is preferable. The amount of the first component of the copolymerization type epoxy resin used is preferably 10% by mass or more, particularly preferably 20% by mass or more, and preferably 70% by mass with respect to the second component of the copolymerization type epoxy resin. % Or less, particularly preferably 50% by mass or less.

  Specific examples of such a copolymer type epoxy resin include “CP-15”, “CP-30”, “CP-50”, “CP-20SA”, “CP-510SA” manufactured by NOF Corporation. , “CP-50S”, “CP-50M”, “CP-20MA” and the like.

  Of the epoxy compounds (a) as described above, bisphenol diglycidyl ethers represented by the above general formula (Ia) are particularly preferable, and the epoxy compound (a-1) is particularly preferable.

  In addition, an epoxy compound (a) may be used individually by 1 type, and may use 2 or more types together. As a combination of two or more epoxy compounds, a combination of an epoxy compound containing two epoxy groups and an epoxy compound containing three or more epoxy groups is preferable. Specifically, a combination of a compound represented by the general formula (Ia) with Nippon Kayaku Co., Ltd. “XD-1000”, Dainippon Ink Co., Ltd. “EXA-7200”, a trisphenolmethane type epoxy compound, etc. Is mentioned.

(Unsaturated group-containing carboxylic acid (b))
As unsaturated group containing carboxylic acid (b), the unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned, As a specific example, (meth) acrylic acid, crotonic acid, o-, m-, p -Monocarboxylic acid such as vinyl benzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substitution, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxy Ethyl adipic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxy Propyl succinic acid, 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (Meth) acryloyloxybutyl hydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid (meth), acrylic acid with ε-caprolactone, β-propiolactone , A monomer to which lactones such as γ-butyrolactone and δ-valerolactone are added, a (meth) acrylic acid dimer, a compound produced by reaction of pentaerythritol tri (meth) acrylate with succinic anhydride, Alternatively, a compound formed by the reaction of pentaerythritol tri (meth) acrylate with phthalic anhydride Etc. The.

  Particularly preferred is (meth) acrylic acid. These may be used alone or in combination of two or more.

(Reaction of epoxy compound (a) with unsaturated group-containing carboxylic acid (b))
As a method of reacting the epoxy group in the epoxy compound (a) with the unsaturated group-containing carboxylic acid (b), a known method can be used. For example, the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b) are mixed with a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, benzyltriethylammonium chloride. Carboxylic acid can be added to an epoxy compound by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours using a quaternary ammonium salt such as pyridine and triphenylphosphine as a catalyst.

  The amount of the catalyst used is preferably 0.01% by mass or more, particularly preferably 0.3% by mass with respect to the reaction raw material mixture (total of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b)). Above, it is preferably 10% by mass or less, particularly preferably 5% by mass or less. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, phenothiazine, etc.). Preferably it is 0.01 mass% or more with respect to a reaction raw material mixture, Most preferably, it is 0.1 mass% or more, Preferably it is 10 mass% or less, Most preferably, it is 5 mass%.

  The proportion of the unsaturated group-containing carboxylic acid (b) added to the epoxy group of the epoxy compound (a) is usually 90 to 100 mol%. Since the remaining epoxy group adversely affects storage stability, the unsaturated group-containing carboxylic acid (b) is usually 0.8 equivalents or more, particularly 0.9 equivalents, relative to 1 equivalent of the epoxy group of the epoxy compound (a). Above, it is preferable to carry out the reaction at a ratio of usually 1.5 equivalents or less, particularly 1.1 equivalents or less.

(Compound (c) having an isocyanate group)
A well-known thing can be used as a compound (c) which has an isocyanate group added to the hydroxyl group of the reaction material of an epoxy compound (a) and unsaturated group containing carboxylic acid (b). This compound (c) may have one isocyanate group in the molecule or may be a polyisocyanate compound having a plurality of isocyanate groups. In order to obtain a resin having a large molecular weight by crosslinking, a polyisocyanate compound is preferably used.

  Examples of the compound having one isocyanate group in the molecule include butane isocyanate, 3-chlorobenzene isocyanate, 4-chlorobenzene isocyanate, cyclohexane isocyanate, benzene isocyanate, 3-isopropenoyl-α, α-dimethylbenzyl isocyanate, m-toluene isocyanate, and the like. Can be mentioned.

  Examples of polyisocyanate compounds include aromatics such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aliphatic diisocyanates such as diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω'- Alicyclic diisocyanates such as diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α ', α'-tetramethyloxy Aliphatic diisocyanate having an aromatic ring such as lylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, Examples thereof include triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, trimers thereof, water adducts, and polyol adducts thereof.

  Of these, preferred are dimers and trimers of organic diisocyanates, and most preferred are trimethylolpropane adducts of tolylene diisocyanate, trimers of tolylene diisocyanate, and trimers of isophorone diisocyanate.

  The compound (c) having an isocyanate group may be used alone or in combination of two or more.

  As a method for producing a trimer of an organic diisocyanate, the above polyisocyanates can be prepared by using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. Examples include a method of obtaining a desired isocyanurate group-containing polyisocyanate by performing partial trimerization, stopping the trimerization by adding a catalyst poison, and then removing unreacted polyisocyanate by solvent extraction and thin-film distillation. .

(Addition of compound (c) having isocyanate group)
The addition ratio of the compound (c) having an isocyanate group is usually 10 mol% or more, preferably 20 mol, of the hydroxyl group produced when the unsaturated group-containing carboxylic acid (b) is added to the epoxy compound (a). % Or more, particularly preferably 30 mol% or more, and usually 95 mol% or less, preferably 90 mol% or less. If this addition rate is too small, the film physical properties may be lowered when it is formed into a coating film, and if it is large, the viscosity of the resulting resin solution increases and handling may be difficult.

  As a method of adding the unsaturated group-containing carboxylic acid (b) to the epoxy compound (a) and then adding the compound (c) having an isocyanate group, a known method can be used. The reaction temperature is usually 40 ° C. or more, preferably 50 ° C. or more, usually 150 ° C. or less, preferably 100 ° C. or less, and the reaction time is usually 1 to 100 hours, preferably 24 hours or less. If the reaction temperature exceeds 130 ° C, polymerization of unsaturated groups occurs in part, leading to a rapid increase in molecular weight, and if it is less than 80 ° C, the reaction may not proceed smoothly.

  In this addition reaction, a catalyst may be used, and a normal urethanization reaction catalyst is used as the catalyst. Examples include tin series such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stanas octoate, iron series such as iron acetylacetonate and ferric chloride, and tertiary amine series such as triethylamine and triethylenediamine. It is done.

(Addition of polybasic acid anhydride (d))
The alkali-soluble unsaturated resin according to the present invention is obtained by adding the compound (c) having an isocyanate group to the hydroxyl group of the reaction product of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b). It is preferable that a polybasic acid anhydride (d) is further added for adjustment.

  As the polybasic acid anhydride (d), known ones can be used. Maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride Dicarboxylic anhydrides such as acid, chlorendic anhydride and methyltetrahydrophthalic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl ether tetracarboxylic acid And tetracarboxylic dianhydrides such as anhydrides. In particular, it is possible to use a dicarboxylic anhydride such as tetrahydrophthalic anhydride or succinic anhydride in combination with a tetracarboxylic dianhydride such as benzophenonetetracarboxylic dianhydride or biphenyltetracarboxylic acid. In the case where a conductive resin composition is formed, it is preferable because good film characteristics are exhibited. When tetracarboxylic dianhydride is used, the acid value may be adjusted or an unsaturated group may be introduced by adding a compound having an active hydrogen group in the molecule to one acid anhydride part. . Among the compounds having an active hydrogen group in the molecule, those having an active hydrogen group and an organic acid group such as citric acid, malic acid, and hydroxypivalic acid can be used as the acid value adjusting application. As an application to introduce groups, unsaturated groups and active hydrogen groups such as hydroxyethyl (meth) acrylic acid, hydroxybutyl (meth) acrylic acid, 2-hydroxymethylacrylic acid methyl ester, 2-hydroxymethylacrylic acid ethyl ester, etc. The thing which has is mentioned.

  The addition rate of the polybasic acid anhydride (d) is usually 5 to 90 mol%, preferably 5 of the hydroxyl group produced when the unsaturated group-containing carboxylic acid (b) is added to the epoxy compound (a). It is -80 mol%, More preferably, it is 5-70 mol%. If the addition rate is too small, the solubility may be insufficient or the adhesion to the substrate may be insufficient.

  As a method of adding the polybasic acid anhydride (d) to the isocyanate compound (c) addition product of the reaction product of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b), a known method is used. Can be used. The reaction temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, and usually 130 ° C. or lower, preferably 125 ° C. or lower. When the reaction temperature exceeds 130 ° C, polymerization of unsaturated groups occurs in part, leading to a rapid increase in molecular weight. If the reaction temperature is less than 80 ° C, the reaction does not proceed smoothly and polybasic acid anhydride (d) may remain. There is.

(Addition of epoxy group-containing compound (e))
The alkali-soluble unsaturated resin in the present invention is obtained by adding a polybasic acid anhydride (d) to the isocyanate compound (c) adduct of the reaction product of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b). After the addition, an epoxy group-containing compound (e) may be further added to a part of the generated carboxyl group.

  In this case, as the epoxy group-containing compound (e), glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, a glycidyl ether compound having a polymerizable unsaturated group, etc. for improving photosensitivity, etc. Alternatively, a glycidyl ether compound having no polymerizable unsaturated group for improving developability can be used, and both of these may be used in combination. Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group or an alkyl group (“Denacol EX-111”, “Denacol EX-121”, “Nagase Chemical Industries Co., Ltd.”), “ Denacol EX-141 "," Denacol EX-145 "," Denacol EX-146 "," Denacol EX-171 "," Denacol EX-192 ").

［式（Ｉ−ｆ）中、Ｘは、下記式（ＩＩ）で表される。

（式（ＩＩ）中、Ｒ^１１〜Ｒ^２６は、それぞれ独立に、水素原子、炭素数１〜１２のアルキル基、又は置換基を有していてもよいフェニル基を示し、Ｒ^１１とＲ^１２、Ｒ^１３とＲ^１４がそれぞれ共にアルキル基の場合は互いに連結して環を形成していてもよい。ｎは０又は１である。）］ (Phenolic hydroxyl group-containing compound (f) having at least two phenolic hydroxyl groups in the molecule)
The phenolic hydroxyl group-containing compound (f) is not particularly limited as long as it has at least two phenolic hydroxyl groups in the molecule. For example, the phenolic hydroxyl group-containing compound represented by the following general formula (If) Is mentioned.

[In the formula (If), X is represented by the following formula (II).

(In formula (II), R ^{11 to} R ²⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group which may have a substituent, and R ¹¹ and R ^12. , When R ¹³ and R ¹⁴ are both alkyl groups, they may be linked to each other to form a ring. N is 0 or 1)]

  In the general formula (If), X has the same meaning as X in the general formula (Ia), and the preferred structure and the like are as described in the description of the general formula (Ia). is there.

(Unsaturated group-containing epoxy compound (g))
The unsaturated group-containing epoxy compound (g) is not particularly limited as long as it has an ethylenically unsaturated double bond and has an epoxy group in the molecule, but acrylates having an epoxy group are preferred. Examples include glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate.

(Reaction of phenolic hydroxyl group-containing compound (f) and unsaturated group-containing epoxy compound (g))
As a method of reacting the phenolic hydroxyl group-containing compound (f) and the unsaturated group-containing epoxy compound (g), a known method can be used. For example, the phenolic hydroxyl group-containing compound (f) and the unsaturated group-containing epoxy compound (g) are combined with a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, benzyl. By using a quaternary ammonium salt such as triethylammonium chloride, pyridine, triphenylphosphine or the like as a catalyst, the reaction is carried out in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours, whereby a phenolic hydroxyl group-containing compound (f) is obtained. An unsaturated group-containing epoxy compound (g) can be added.

  The amount of the catalyst used is preferably 0.01% by mass or more, particularly preferably 0.1% by mass or more, based on the reaction raw material mixture (the total of the phenolic hydroxyl group-containing compound (f) and the unsaturated group-containing epoxy compound (g)). It is 3% by mass or more, preferably 10% by mass or less, and particularly preferably 5% by mass or less. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, phenothiazine, etc.). Preferably it is 0.01 mass% or more with respect to a reaction raw material mixture, Most preferably, it is 0.1 mass% or more, Preferably it is 10 mass% or less, Most preferably, it is 5 mass%.

  The ratio of the unsaturated group-containing epoxy compound (g) to be reacted with the phenolic hydroxyl group-containing compound (f) is usually 90 to 120 mol%. Since the residual epoxy group adversely affects storage stability, the phenolic hydroxyl group-containing compound (f) is usually 0.8 equivalents or more, particularly 0 equivalents to 1 equivalent of the epoxy group of the unsaturated group-containing epoxy compound (g). It is preferable to carry out the reaction at a ratio of 0.9 equivalent or more and usually 1.5 equivalent or less, particularly 1.2 equivalent or less.

(Addition of compound (c) having isocyanate group, addition of polybasic acid anhydride (d), addition of epoxy group-containing compound (e))
Addition of compound (c) having an isocyanate group to the reaction product of phenolic hydroxyl group-containing compound (f) and unsaturated group-containing epoxy compound (g), addition of polybasic acid anhydride (d), epoxy group Each of the additions of the containing compound (e) has an isocyanate group to the reaction product of the epoxy compound (a) having at least two epoxy groups in the molecule and the unsaturated group-containing carboxylic acid (b). The addition can be performed in the same manner as the addition of the compound (c), the addition of the polybasic acid anhydride (d), and the addition of the epoxy group-containing compound (e).

(Physical properties of alkali-soluble unsaturated resins)
The polystyrene-converted mass average molecular weight (Mw) measured by GPC of the alkali-soluble unsaturated resin in the present invention obtained as described above is usually 700 or more, preferably 1000 or more, and usually 50000 or less, preferably 30000 or less. . If the mass average molecular weight of the alkali-soluble unsaturated resin is too small, the heat resistance and the film strength are inferior, and if it is too large, the solubility in the developer is insufficient.

  Further, the acid value (mg-KOH / g) of the alkali-soluble unsaturated resin in the present invention is usually 10 or more, preferably 30 or more, and usually 200 or less, preferably 150 or less. If the acid value of the alkali-soluble unsaturated resin is too low, sufficient solubility cannot be obtained, and if the acid value is too high, curability is insufficient and surface properties are deteriorated.

<Photopolymerization initiator>
The photosensitive resin composition of the present invention may further contain a photopolymerization initiator.

  The photopolymerization initiator used in the present invention is not particularly limited as long as it is a compound that polymerizes an ethylenically unsaturated group with actinic rays, but the photosensitive resin composition of the present invention has ethylene as a compound having a polymerizable group. In the case of containing a photoactive compound, it is preferable to use a photopolymerization initiator that directly absorbs light or is photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.

  Specific examples of the photopolymerization initiator that can be used in the present invention are listed below. 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, halomethylated triazine derivatives such as 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine; 2 -Trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5-[[beta]-(2'-benzofuryl) vinyl] -1,3,4-oxadi Azole, -trichloromethyl-5- [β- (2 '-(6 "-benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5 Halomethylated oxadiazole derivatives such as ril-1,3,4-oxadiazole; 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl)- 4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4, Imidazole derivatives such as 5-diphenylimidazole dimer and (4′-methoxyphenyl) -4,5-diphenylimidazole dimer; benzoin alkyl such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether Ethers; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t- Anthraquinone derivatives such as tilanthraquinone and 1-chloroanthraquinone; benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone and 2-carboxybenzophenone; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1 , 1-trichloromethyl- (p-butylphenyl) ketone and other acetophenone derivatives; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diisopropylthioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine; Phenazine derivatives such as 9,10-dimethylbenzphenazine; anthrone derivatives such as benzanthrone; dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bisphenyl, di Clopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1 -Yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, dicyclopentadienyl-Ti-2,6-diplorophen-1-yl, dicyclopentadienyl -Ti-2,4-difluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl-Ti -Titanocene derivatives such as bis-2,6-difluorophen-1-yl, dicyclopentagenyl-Ti-2,6-difluoro-3- (pyr-1-yl) -phen-1-ylFurther, oxime initiators described in JP-A-2000-80068 can be used particularly preferably.

  In addition, photopolymerization initiators that can be used in the present invention are described in Fine Chemical, March 1, 1991, Vol. 20, no. 4, P. 16-P26, JP-A-59-152396, JP-A-61-151197, JP-B-45-37377, JP-A-58-40302, JP-A-10-39503 Has been.

<Color material>
The photosensitive resin composition of the present invention may be a photosensitive colored resin composition further containing a coloring material.

  As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like. As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is. Specific examples of pigments that can be used are shown below by pigment numbers. Note that terms such as “CI Pigment Red 2” mentioned below mean a color index (CI).

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

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

  Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. And CI pigment oranges 38 and 71.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

  Further, when the photosensitive resin composition of the present invention is a photosensitive colored resin composition for a resin black matrix of a color filter, a black color material can be used as the color material. The black color material may be a single black color material or a mixture of red, green, blue, and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, it is preferable to use the pigment dispersed in an average particle size of 1 μm or less, preferably 0.5 μm or less.

  Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean the color index (CI)).

  Further, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

  Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black.

  Among these, carbon black and titanium black are particularly preferable from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black.

  Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45 # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B

  Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, C lor Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

  Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130 , VULCAN XC72R, ELFTEX-8

  Made by Colombian Carbon: Raven11, Raven14, Raven15, Raven16, Raven22, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10 , RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

  As a method for producing titanium black, a mixture of titanium dioxide and titanium metal is heated and reduced in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, No. 61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), and the like. It is not something.

  Examples of commercially available titanium black include Titanium Black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.

  As examples of other black pigments, titanium black, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments.

  In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, or the like can also be used as the pigment.

  These various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

  The average particle size of these pigments is usually 1 μm, preferably 0.5 μm or less, more preferably 0.25 μm or less. Examples of dyes that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

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

  Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.

  Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

<Dispersant>
When the photosensitive resin composition of the present invention is a photosensitive colored resin composition containing a coloring material, the photosensitive colored resin composition may further contain a dispersant.

The dispersant used in the present invention is preferably a nitrogen atom-containing dispersant. As the nitrogen atom-containing dispersant, surfactants, polymer dispersants and the like are usually used, and polymer dispersants are particularly suitable. As a polymer dispersant,
[1] Urethane dispersant [2] Graft copolymer containing nitrogen atom [3] A block consisting of A block having quaternary ammonium base in side chain and B block having no quaternary ammonium base, It is preferable to contain at least one of a -B block copolymer and / or a B-A-B block copolymer. A dispersing agent may be used individually by 1 type, or 2 or more types may be mixed and used for it.

  In the present invention, a coating film formed from the photosensitive colored resin composition while maintaining dispersion stability by using a combination of these nitrogen atom-containing dispersant and the specific alkali-soluble unsaturated resin described above. It is possible to achieve high adhesion at the time of development between the substrate and the substrate and suppression of remaining undissolved substances.

  The form of the nitrogen atom in the nitrogen atom-containing dispersant is preferably an amino group, a quaternary ammonium salt, or the like. This is because these functional groups usually have basicity so that they easily coordinate with acidic groups such as pigments and pigment derivatives, and as a result, contribute to dispersion stabilization. The amine value of the dispersant is usually 2 mg-KOH / g or more, preferably 3 mg-KOH / g or more, and usually 100 mg-KOH / g or less, preferably 80 mg-KOH / g or less. When the amine value is too low, the basicity is insufficient and the dispersion stability is poor, and when the amine value is too high, when used in a liquid crystal display device, the voltage holding ratio of the liquid crystal is lowered, and as a result, display defects are likely to occur. It is not preferable.

Next, a preferable dispersant will be described in detail.
[1] Urethane-based dispersant The urethane-based dispersant includes (1) a polyisocyanate compound, (2) a compound having one or two hydroxyl groups in the same molecule, and (3) active hydrogen and tertiary in the same molecule. A dispersion resin obtained by reacting with a compound having an amino group is preferred.

(1) Polyisocyanate compound Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, Aromatic diisocyanates such as tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) , Ω, ω′-diisocyanate dimethylcyclohexane and the like, alicyclic diisocyanates, xylylene diisocyanate, α, aliphatic diisocyanates having an aromatic ring such as α, α ′, α′-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, Triisocyanates such as 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, and trimers thereof, water adducts, and polyols thereof Examples include adducts. Preferred as the polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These can be used alone or in combination of two or more. Also good.

  As a method for producing a trimer of an organic diisocyanate, the polyisocyanate is formed by using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. Examples include a method of obtaining a desired isocyanurate group-containing polyisocyanate by performing partial trimerization, stopping the trimerization by adding a catalyst poison, and then removing unreacted polyisocyanate by solvent extraction and thin-film distillation. .

(2) Compounds having one or two hydroxyl groups in the same molecule Examples of compounds having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and these compounds. In which one terminal hydroxyl group is alkoxylated with an alkyl group having 1 to 25 carbon atoms. These may be used alone or in combination of two or more.

  Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned. Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4- Nanthanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N -N-alkyl dialkanolamines such as methyldiethanolamine) obtained by polycondensation, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diol or carbon number 1 to 25 monovalent Polylactone diol or polylactone monool obtained by using an alcohol as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone starting with an alcohol having 1 to 25 carbon atoms, more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to a monool. .

  Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of the polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Of the compounds having one or two hydroxyl groups in the same molecule, polyether glycol and polyester glycol are particularly preferable.

  The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 or more, preferably 500 or more, more preferably 1,000 or more, and usually 10,000 or less, preferably 6,000 or less, More preferably, it is 4,000 or less.

(3) Compound having active hydrogen and tertiary amino group in the same molecule Active hydrogen, that is, hydrogen atom directly bonded to oxygen atom, nitrogen atom or sulfur atom includes hydroxyl group, amino group, thiol group, etc. The hydrogen atom in a functional group is mentioned, Especially, the hydrogen atom of an amino group, especially a primary amino group is preferable.

  The tertiary amino group is not particularly limited. For example, a dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, isopropyl and n-butyl, or the dialkylamino group is linked to form a heterocyclic structure. The group which forms, More specifically, an imidazole ring or a triazole ring is mentioned.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  In addition, the tertiary amino group is a nitrogen-containing heterocycle, such as pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include N-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring, nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, and isoquinoline ring. Preferred as these nitrogen-containing heterocycles are an imidazole ring or a triazole ring.

  Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. . Specific examples of the compound having a triazole ring and a primary amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H- 1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino- Examples include 1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole Is preferred.

  A preferable blending ratio of the urethane-based dispersed resin raw material is usually 10 parts by mass or more, preferably 20 parts by mass or more, more preferably, a compound having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound. 30 parts by mass or more, usually 200 parts by mass or less, preferably 190 parts by mass or less, more preferably 180 parts by mass or less, and the compound having an active hydrogen and a tertiary amino group in the same molecule is usually 0.2 parts by mass or more, Preferably it is 0.3 mass part or more, and is 25 mass parts or less normally, Preferably it is 24 mass parts or less.

  The polystyrene-reduced mass average molecular weight measured by GPC of the urethane-based dispersion resin according to the present invention is usually 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, and usually 200,000 or less, preferably Is in the range of 100,000 or less, more preferably 50,000 or less. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility is lowered, and the dispersibility is inferior and the reaction is difficult to control.

  The production of the urethane-based dispersion resin in the present invention is performed according to a known method for producing a polyurethane resin. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used.

  Moreover, a normal urethanization reaction catalyst is used as a catalyst at the time of manufacture. Examples include tin series such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stanas octoate, iron series such as iron acetylacetonate and ferric chloride, and tertiary amine series such as triethylamine and triethylenediamine. It is done.

  The amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is 1 mg-KOH / g or more, particularly 5 mg-KOH / g or more and 100 mg-KOH / g or less in terms of amine value of the dispersion resin after the reaction. In particular, it is preferable to control within the range of 95 mg-KOH / g or less. When the amine value is less than the above range, the dispersing ability tends to decrease, and when it exceeds the above range, the developability tends to decrease. In addition, when an isocyanate group remains in the dispersion resin by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the dispersion resin has high temporal stability.

[2] Graft copolymer containing nitrogen atom The graft copolymer containing a nitrogen atom is preferably one having a repeating unit containing a nitrogen atom in the main chain. Especially, it is preferable to have a repeating unit represented by the following general formula (i) or / and a repeating unit represented by the following general formula (ii).

（一般式（ｉ），（ｉｉ）中、Ｒ^４１は、メチレン、エチレン、プロピレン等の直鎖状又は分岐状の炭素数１〜５のアルキレン基を表し、好ましくは炭素数２〜３のアルキレン基であり、更に好ましくはエチレン基である。Ａは水素原子又は下記一般式（ｉｉｉ）〜（ｖ）のいずれかを表すが、好ましくは下記一般式（ｉｉｉ）である。）

（一般式（ｉｉｉ）中、Ｗ^１は炭素数２〜１０の直鎖状又は分岐状のアルキレン基を表し、中でもブチレン、ペンチレン、ヘキシレン等の炭素数４〜７のアルキレン基が好ましい。ｐは１〜２０の整数を表し、好ましくは５〜１０の整数である。）

（一般式（ｉｖ）中、Ｇ^１は２価の連結基を表し、中でもエチレン、プロピレン等の炭素数１〜４のアルキレン基とエチレンオキシ、プロピレンオキシ等の炭素数１〜４のアルキレンオキシ基が好ましい。Ｗ^２はエチレン、プロピレン、ブチレン等の直鎖状又は分岐状の炭素数２〜１０のアルキレン基を表し、中でもエチレン、プロピレン等の炭素数２〜３のアルキレン基が好ましい。Ｇ^２は水素原子又は−ＣＯ−Ｒ^４２（Ｒ^４２はエチル、プロピル、ブチル、ペンチル、ヘキシル等の炭素数１〜１０のアルキル基を表し、中でもエチル、プロピル、ブチル、ペンチル等の炭素数２〜５のアルキル基が好ましい）を表す。ｑは、１〜２０の整数を表し、好ましくは５〜１０の整数である。）

（一般式（ｖ）中、Ｗ^３は炭素数１〜５０のアルキル基又は水酸基を１〜５有する炭素数１〜５０のヒドロキシアルキル基を表し、中でもステアリル等の炭素数１０〜２０のアルキル基、モノヒドロキシステアリル等の水酸基を１〜２個有する炭素数１０〜２０のヒドロキシアルキル基が好ましい。）

(In the general formulas (i) and (ii), R ⁴¹ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably an alkylene having 2 to 3 carbon atoms. A group, more preferably an ethylene group, A represents a hydrogen atom or any one of the following general formulas (iii) to (v), preferably the following general formula (iii).

(In general formula (iii), W ¹ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and among them, an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene, and hexylene is preferable. Represents an integer of 1 to 20, preferably an integer of 5 to 10.)

(In General Formula (iv), G ¹ represents a divalent linking group, and in particular, an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene, and an alkyleneoxy group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy. preferably .W ² represents ethylene, propylene, a linear or branched alkylene group having 2 to 10 carbon atoms butylene, among which ethylene, an alkylene group having 2 to 3 carbon atoms such as propylene preferred .G ² Represents a hydrogen atom or —CO—R ⁴² (R ⁴² represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, etc., among them, C 2-5 such as ethyl, propyl, butyl, pentyl, etc. Q represents an integer of 1 to 20, preferably an integer of 5 to 10.)

(In General Formula (v), W ³ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms having 1 to 5 hydroxyl groups, and in particular, an alkyl group having 10 to 20 carbon atoms such as stearyl. C1-C20 hydroxyalkyl groups having 1-2 hydroxyl groups such as monohydroxystearyl are preferred.)

The content of the repeating unit represented by the general formula (i) or (ii) in the graft copolymer of the present invention is preferably higher, and is generally 50 mol% or more in total, preferably 70 mol% or more. is there. The repeating unit represented by the general formula (i) and the repeating unit represented by the general formula (ii) may both be present, and the content ratio is not particularly limited, but is preferably the general formula ( It is preferable that the repeating unit i) is contained in a larger amount. The total number of repeating units represented by general formula (i) or general formula (ii) in the graft copolymer is 1 or more, preferably 10 or more, more preferably 20 or more, and usually 100 or less, preferably 70. Hereinafter, it is more preferably 50 or less. Further, the graft copolymer may contain a repeating unit other than the general formula (i) and the general formula (ii), and examples of the other repeating unit include an alkylene group and an alkyleneoxy group. The graft copolymer in the present invention preferably has —NH ₂ and —R ⁴¹ —NH ₂ (R ⁴¹ is as defined in formulas (i) and (ii)) at the ends.

  In the case of the graft copolymer as described above, the main chain may be linear or branched.

  The weight average molecular weight of the graft copolymer measured by GPC is preferably 3,000 or more, particularly 5,000 or more, and preferably 100,000 or less, particularly 50,000 or less. If the mass average molecular weight is less than 3,000, the color material cannot be aggregated, and may increase in viscosity or gel. If it exceeds 100,000, the viscosity itself increases. This is not preferable because the solubility in an organic solvent is insufficient.

  As a method for synthesizing the dispersing agent, a known method can be employed. For example, a method described in JP-B-63-30057 can be used.

[3] AB block copolymer and / or BAB block copolymer comprising A block having quaternary ammonium base in side chain and B block not having quaternary ammonium base The A block constituting the block copolymer of the agent is a quaternary ammonium base, preferably -N ⁺ R ^1a R ^2a R ^3a · Y ⁻ (where R ^1a , R ^2a and R ^3a are each independently hydrogen An atom or an optionally substituted cyclic or chain hydrocarbon group, or two or more of R ^1a , R ^2a and R ^3a may be bonded to each other to form a cyclic structure. Y ⁻ represents a counter anion.) And has a quaternary ammonium base. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

In -N ⁺ R ^1a R ^2a R ^3a , as a cyclic structure formed by combining two or more of R ^1a , R ^2a and R ^3a with each other, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or A condensed ring formed by condensing two of these may be mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following.

（式中、ＲはＲ^１ａ〜Ｒ^３ａのうちいずれかの基を表す。）

(In the formula, R represents any one of R ^{1a to} R ^3a .)

  These cyclic structures may further have a substituent.

As ^R 1a ^{to R 3a} in the ^{-N + R 1a R 2a R 3a} , and more preferably may have an alkyl group, or a substituent having carbon atoms of 1 to 3 may have a substituent It is a phenyl group.

  As the A block, those containing a partial structure represented by the following general formula (1) are particularly preferable.

（一般式（２）中、Ｒ^１ａ、Ｒ^２ａ、Ｒ^３ａは各々独立に、水素原子、又は置換されていてもよい環状若しくは鎖状の炭化水素基を表す。或いは、Ｒ^１ａ、Ｒ^２ａ及びＲ^３ａのうち２つ以上が互いに結合して、環状構造を形成していてもよい。Ｒ^４ａは、水素原子又はメチル基を表す。Ｑは、２価の連結基を表し、Ｙ⁻は、対アニオンを表す。）

(In General Formula (2), R ^1a , R ^2a and R ^3a each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, R ^1a , R ^2a and Two or more of R ^3a may be bonded to each other to form a cyclic structure, R ^4a represents a hydrogen atom or a methyl group, Q represents a divalent linking group, and Y ⁻ represents Represents a counter anion.)

In the general formula (2), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R ^5a —, —COO—R ^6a — (provided that R ^5a and R ^6a is a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R ^7a —O—R ^8a —: R ^7a and R ^8a are each independently an alkylene group). And the like, and preferably —COO—R ^6a —.

Examples of Y ⁻ of the counter anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ^{− and the} like.

  Two or more kinds of partial structures containing the specific quaternary ammonium base as described above may be contained in one A block. In that case, two or more quaternary ammonium base-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base may be contained in the A block, and examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later. It is done. The content of the partial structure containing no quaternary ammonium base in the A block is preferably 0 to 50% by mass, more preferably 0 to 20% by mass. Most preferably, it is not included in the A block.

  On the other hand, examples of the B block constituting the dispersant block copolymer include styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid. Propyl, isopropyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, N, N-dimethylaminoethyl (meth) (Meth) acrylic acid ester monomers such as acrylate; (meth) acrylic acid monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N, N- Dimethylaminoethylacrylami Vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether, (meth) acrylamide-based monomers like N- methacryloyl morpholine, polymer structure obtained by copolymerizing comonomers like.

  The B block is preferably a partial structure derived from a (meth) acrylic acid ester monomer represented by the following general formula (3).

（一般式（３）中、Ｒ^９ａは、水素原子又はメチル基を表す。Ｒ^１０ａは、置換基を有していてもよい環状又は鎖状のアルキル基、置換基を有していてもよいアリル基、又は置換基を有していてもよいアラルキル基を表す。）

(In General Formula (3), R ^9a represents a hydrogen atom or a methyl group. R ^10a may have a cyclic or chain alkyl group which may have a substituent, or a substituent. Represents an allyl group or an aralkyl group which may have a substituent.)

  Two or more kinds of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block. Of course, the B block may further contain a partial structure other than these. When a partial structure derived from two or more types of monomers is present in a B block that does not contain a quaternary ammonium base, each partial structure is contained in either mode of random copolymerization or block copolymerization in the B block. May be. When the B block contains a partial structure other than the partial structure derived from the (meth) acrylate monomer, the content in the B block of the partial structure other than the (meth) acrylate monomer is preferably Is 0 to 50% by mass, more preferably 0 to 20% by mass, but it is most preferable that a partial structure other than the (meth) acrylic acid ester monomer is not included in the B block.

  The dispersant used in the present invention is an AB block or a B-A-B block copolymer type polymer compound composed of such an A block and a B block. Such a block copolymer is, For example, it is prepared by the living polymerization method shown below.

  The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. In the anion living polymerization method, the polymerization active species is an anion, for example, shown in the following scheme.

の場合、

in the case of,

  In the radical living polymerization method, the polymerization active species is a radical, and is represented by the following scheme, for example.

の場合、

in the case of,

の場合、

in the case of,

  In synthesizing such a dispersant, JP-A-9-62002 and P.I. Lutz, P.M. Masson et al, Polym. Bull. 12, 79 (1984), B.R. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K .; Ute, et al, Polym. J. et al. 17, 977 (1985), 18, 1037 (1986), Koichi Right-hand, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Thesis, 46, 189 (1989), M.M. Kuroki, T .; Aida, J .; Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.C. Y. Sogoh, W.H. R. The well-known method as described in Hertler et al, Macromolecules, 20, 1473 (1987) etc. can be employ | adopted.

  Whether the dispersant used in the present invention is an AB block copolymer or a B-A-B block copolymer, the A block / B block ratio (mass ratio) constituting the copolymer. Is usually in the range of 1/99 or more, especially 5/95 or more, and usually 80/20 or less, especially 60/40 or less. Outside this range, it may not be possible to combine good heat resistance and dispersibility.

  In addition, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and the BAB block copolymer used in the present invention is usually preferably 0.1 to 10 mmol. In some cases, good heat resistance and dispersibility cannot be combined. Such a block copolymer usually contains an amino group produced in the production process, but its amine value is about 1 to 100 mg-KOH / g. The amine value is a value expressed in mg of KOH corresponding to the acid value after neutralization titration of a basic amino group with an acid.

  Moreover, although the acid value of this block copolymer depends on the presence and type of the acid group that is the basis of the acid value, it is generally preferable that the acid value is low, and is usually 10 mg-KOH / g or less, and its molecular weight is The mass average in terms of polystyrene is usually preferably 1000 or more and 100,000 or less. When the molecular weight of the block copolymer is less than 1,000, the dispersion stability decreases, and when it exceeds 100,000, the developability and resolution tend to decrease.

  In the present invention, it is preferable to contain a phosphate ester type dispersant in addition to the block copolymer. This improves the solubility during development.

  The phosphate ester may be any of primary to tertiary esters, but primary esters are preferred from the viewpoint of dispersion performance. As for the structure of the part couple | bonded with phosphoric acid, the structure which has a hydroxyl group at the terminal represented by polyethers, such as polyester, such as polycaprolactone, and polyethyleneglycol, is mentioned, for example. These may be a copolymer of polyester and polyether. Further, it may have a double bond such as (meth) acrylate at one end of the polyester chain and / or the polyether chain, and may form a copolymer with another radical polymerizable compound.

  Specifically, the phosphate ester preferably has a partial structure represented by the following structural formula (4).

  Such phosphoric acid esters can be produced, for example, by the methods described in JP-B-50-22536 and JP-A-58-128393.

  The molecular weight Mw of the phosphate ester type dispersant is usually 200 or more, and usually 5000 or less, preferably 1000 or less. Since this phosphate ester type dispersant is originally added for the purpose of imparting development solubility, it is not preferable to have a high molecular weight.

<Photopolymerizable monomer>
In the photosensitive resin composition of the present invention, it is preferable to use a photopolymerizable monomer (photopolymerizable compound) in addition to the photopolymerization initiator in view of sensitivity and the like. Examples of the photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group. Specific examples of the compound having an ethylenically unsaturated group in the molecule include (meth) acrylic acid, alkyl ester of (meth) acrylic acid, acrylonitrile, styrene, carboxylic acid having one ethylenically unsaturated bond and many ( And monoesters of monohydric alcohols.

  As the photopolymerizable monomer, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. Examples of such polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatics Examples thereof include esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a polyhydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.

  Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. In the same way, itaconic acid ester instead of itaconate, Crotonic acid esters instead of, or maleic acid esters in which instead of the maleate and the like.

  Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. Etc.

  The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but typical examples include acrylic acid, phthalic acid, and ethylene. Condensates of glycols, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

  In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted. Urethane (meth) acrylates as obtained; epoxy acrylates such as addition reaction product of polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate Allyl esters such as: vinyl group-containing compounds such as divinyl phthalate are useful.

<Other ingredients of the photosensitive resin composition>
In addition to the above-mentioned components, the photosensitive resin composition of the present invention is appropriately mixed with an organic solvent, an adhesion improver, a coating improver, a development improver, an ultraviolet absorber, an antioxidant, a silane coupling agent, and the like. be able to.

(1) Organic solvent Although there is no restriction | limiting in particular as an organic solvent, For example, diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate , N-octane, Barsol # 2, Apco # 18 solvent, diisobutylene, amyl acetate, butyl butyrate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, Social solvent No. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, butyl acetate (n, sec, t), hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amylformate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methylamino Ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3- Ethoxypropionic acid , Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, dipropylene glycol monomethyl ether, ethylene glycol acetate, ethyl carb Specific organic solvents such as Tol, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate Can be mentioned.

  The solvent is capable of dissolving or dispersing each component, and it is preferable to select a solvent having a boiling point in the range of 100 to 250 ° C. More preferably, it has a boiling point of 120-170 ° C. These may be used alone or in combination of two or more.

(2) Silane coupling agent In order to improve the adhesion to the substrate, a silane coupling agent can be added. Various types of silane coupling agents such as epoxy, methacrylic, amino and the like can be used, and epoxy silane coupling agents are particularly preferable.

<Method for producing photosensitive resin composition>
The photosensitive resin composition of this invention is manufactured in accordance with a conventional method.

  For example, in the case of a photosensitive colored resin composition containing a color material, first, a predetermined amount of each of the color material, the solvent, and the dispersant is weighed, and in the dispersion treatment step, the color material is dispersed to form a liquid colored composition ( Ink-like liquid). In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By performing this dispersion treatment, the color material is made fine particles, so that the coating characteristics of the photosensitive colored resin composition are improved, and the transmittance of the product color filter substrate is improved.

  When dispersing the color material, the above alkali-soluble unsaturated resin may be used in combination. For example, when the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature for the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. The dispersion time varies depending on the composition of the ink-like liquid (coloring material, solvent, dispersant), the size of the sand grinder apparatus, and the like.

  To the ink-like liquid obtained by the dispersion treatment, a solvent, a compound represented by the above formula (1), an alkali-soluble unsaturated resin, a photopolymerization initiator, and in some cases other components other than the above are mixed, Make a uniform dispersion. In addition, in each process of a dispersion | distribution process and mixing, since fine refuse may mix, it is preferable to filter the obtained photosensitive colored resin composition with a filter etc.

  The photosensitive resin composition which does not contain a color material can be manufactured by mixing each component without performing the dispersion process of the color material in the manufacturing method of the said photosensitive coloring resin composition.

<Ingredient compounding amount in photosensitive resin composition>
The compounding amount of the compound represented by the formula (1) is usually 1% by mass or more, preferably 3% by mass or more, and usually 10% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Hereinafter, it is preferably 5% by mass or less. By setting it as said range, a favorable micro patterning characteristic can be acquired, obtaining favorable developability.
The compounding quantity of alkali-soluble unsaturated resin is normally 10 mass% or more with respect to the total solid of the photosensitive resin composition of this invention, Preferably it is 20 mass% or more, Usually 80 mass% or less, Preferably it is 70. It is below mass%. When the photosensitive resin composition of the present invention is a photosensitive colored resin composition containing a color material, the ratio of the alkali-soluble unsaturated resin to the color material is usually 5% by mass or more, preferably 10% by mass. Above, it is 500 mass% or less normally, Preferably it is the range of 200 mass% or less. If the content of the alkali-soluble unsaturated resin is too small, the solubility of the unexposed portion in the developing solution is lowered, and it is easy to induce development failure. Conversely, if the content is large, it is difficult to obtain a desired pixel film thickness.

  In the present invention, the “total solid content” means all components other than the solvent, and the total solid content in the photosensitive resin composition of the present invention is usually 10% by mass or more and 90% by mass or less. .

  When blending a photopolymerization initiator, the content thereof is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably, based on the total solid content of the photosensitive resin composition of the present invention. It is 0.7 mass% or more, and is 30 mass% or less normally, Preferably it is 20 mass% or less. If the content of the photopolymerization initiator is too small, the sensitivity may be lowered. On the other hand, if the content is too large, the solubility of the unexposed part in the developer is lowered, and development failure tends to be induced.

  When mix | blending a coloring material, the content can be normally selected in the range of 1-70 mass% with respect to the total solid content in the photosensitive coloring resin composition of this invention. In this range, 10 to 70 mass% is more preferable, and 20 mass% or more and 60 mass% or less is particularly preferable. If the content of the color material is too small, the film thickness with respect to the color density becomes too large, which adversely affects the gap control and the like when forming a liquid crystal cell. On the other hand, if the content of the color material is too large, sufficient image formability may not be obtained.

  In the case where a dispersant is blended, and among the nitrogen atom-containing dispersants, when the above [1] urethane-based dispersion resin is used, the content relative to the color material component in the photosensitive colored resin composition is usually 10 masses. % Or more, preferably 20% by mass or more, particularly preferably 30% by mass or more, and usually 300% by mass or less, preferably 100% by mass or less, particularly preferably 80% by mass or less. If the amount of the nitrogen atom-containing dispersant is too small, adsorption to the coloring material is insufficient, aggregation cannot be prevented, and viscosity or gelation may occur. On the other hand, if the amount is too large, the film thickness increases. In this case, after the color filter is formed, cell gap control failure in the liquid crystal cell forming process may occur.

  Further, when the above-mentioned [2] graft copolymer is used as a dispersant, the content relative to the color material component in the photosensitive colored resin composition is usually 10% by mass or more, preferably 20% by mass or more, particularly preferably. It is 30% by mass or more, usually 300% by mass or less, preferably 100% by mass or less, and particularly preferably 80% by mass or less. If the amount of the dispersant component is too small, the adsorption to the coloring material is insufficient, aggregation cannot be prevented, and the viscosity or gelation may occur. On the other hand, if the amount is too large, the film thickness becomes too thick. After the color filter is formed, cell gap control failure may occur in the liquid crystal cell forming process, which is not preferable.

  When the above [3] block copolymer is used as a dispersant, the content relative to the color material component in the photosensitive colored resin composition is usually 10% by mass or more, preferably 20% by mass or more, and particularly preferably. It is 30% by mass or more, usually 300% by mass or less, preferably 100% by mass or less, and particularly preferably 80% by mass or less. If the amount of the dispersant component is too small, the adsorption to the coloring material is insufficient, aggregation cannot be prevented, and the viscosity or gelation may occur. On the other hand, if the amount is too large, the film thickness becomes too thick. After the color filter is formed, cell gap control failure may occur in the liquid crystal cell forming process, which is not preferable.

  The phosphate ester type dispersant is usually 5 parts by mass or more, preferably 10 parts by mass or more, and usually 100 parts by mass or less, preferably 80 parts per 100 parts by mass of the [3] block copolymer. It is preferable to use it at a mass part or less. If the proportion of the phosphate ester type dispersant is too small, sufficient development solubility may not be exhibited. On the other hand, if the proportion of the phosphate ester type dispersant is too large, the effect is saturated and the dispersibility may be lowered.

  When using a photopolymerizable monomer, the content is 90 mass% or less normally with respect to the total solid of the photosensitive resin composition of this invention, Preferably it is 80 mass% or less. When there is too much content of a photopolymerizable monomer, the permeability of the developing solution to an exposed part will become high and it will become difficult to obtain a favorable image. In addition, the minimum of content of a photopolymerizable monomer is 0 mass% or more normally, Preferably it is 5 mass% or more.

<Use of photosensitive resin composition>
The photosensitive resin composition of the present invention is useful as a photosensitive resin composition for image formation, black matrix, overcoat, rib, and spacer for color filters used in liquid crystal panels such as liquid crystal displays. Further, the photosensitive resin composition of the present invention is used for solder resists for flexible printed wiring boards, plating resists, correlated insulating films for multilayer printed wiring boards, photosensitive optical waveguides, and photocurable liquid crystal sealing materials in addition to color filter applications. It is useful as a photocurable EL sealing material, a photocurable adhesive, and the like.

[Color filter]
The color filter of the present invention can be produced by providing a black matrix on a transparent substrate and usually forming red, green, and blue pixel images, and the photosensitive colored resin composition of the present invention including a coloring material. The product is used as at least one resist forming coating solution of black, red, green, and blue. For black resist, on the transparent glass substrate glass surface, for red, green and blue, on the resin black matrix forming surface formed on the transparent substrate, or metal black formed using a chromium compound or other light shielding metal material A pixel image of each color is formed on the matrix forming surface by performing coating, heat drying, image exposure, development, and thermosetting. In addition, the photosensitive resin composition of the present invention that does not contain a coloring material is used as a photosensitive resin composition for overcoats, ribs, and spacers.

  The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, polysulfone thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, and poly (meth) acrylic. Examples thereof include thermosetting resin sheets such as a resin, or various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.

  For transparent substrates and black matrix forming substrates, for improvement of surface properties such as adhesion, corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents and urethane resins, etc. May be performed.

  The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

[1] Black matrix The black matrix is formed on a transparent substrate using a light-shielding metal thin film or a photosensitive colored resin composition for a resin black matrix. As the light shielding metal material, chromium compounds such as metal chromium, chromium oxide and chromium nitride, nickel and tungsten alloy, and the like may be used, and these may be laminated in a plurality of layers.

  These metal light shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape with a positive photoresist, ceric ammonium nitrate, perchloric acid and / or nitric acid are added to chromium. Other materials are etched using an etching solution according to the material, and finally a positive photoresist is stripped with a special stripping agent to form a black matrix. be able to.

  In this case, first, a thin film of the metal or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, after forming a coating film of the photosensitive colored resin composition on this thin film, the coating film is exposed and developed using a photomask having a repetitive pattern such as stripes, mosaics, and triangles to form a resist image. . Thereafter, this coating film can be etched to form a black matrix.

  When using the photosensitive colored resin composition for resin black matrix, the black matrix is formed using the photosensitive colored resin composition of the present invention containing a black coloring material. For example, a black color material such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black or the like, or a red, green, blue, or the like appropriately selected from inorganic or organic pigments and dyes A black matrix can be formed in the same manner as described below for forming a red, green, and blue pixel image using a photosensitive colored resin composition containing a black color material by mixing.

[2] Pixels A photosensitive colored resin composition containing a color material of one color of red, green, and blue is applied on a transparent substrate provided with a black matrix, dried, and then a photomask is formed on the coating film. Overlaid, a pixel image is formed through this photomask by image exposure, development, and if necessary, heat curing or photocuring to form a colored layer. A color filter image can be formed by performing this operation for each of the three colored photosensitive colored resin compositions of red, green, and blue.

(2-1) Coating method Coating of the photosensitive colored resin composition for the color filter can be performed by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, and there is no influence of mist adhering when using the spin coating method, so that the generation of foreign matter is suppressed. To preferred.

  If the thickness of the coating film is too thick, pattern development becomes difficult, and gap adjustment in the liquid crystal cell forming process may be difficult. If it is too thin, it is difficult to increase the pigment concentration, and desired color expression is achieved. May become impossible. The thickness of the coating film is preferably in the range of 0.2 to 20 μm, more preferably in the range of 0.5 to 10 μm, and still more preferably in the range of 0.5 to 5 μm, as the film thickness after drying. It is a range.

(2-2) Drying method It is preferable to dry the coating film after applying the photosensitive colored resin composition to the substrate by a drying method using a hot plate, an IR oven, or a convection oven. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably 50 to 130 ° C., depending on the type of the solvent component, the performance of the dryer used, and the like. It is selected in the range of 30 seconds to 3 minutes.

  The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, when the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.

(2-3) Exposure method Image exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive colored resin composition and irradiating a UV or visible light source through this mask pattern. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. As the light source, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser, Examples thereof include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

(2-4) Development Method The color filter according to the present invention is a film formed of a photosensitive colored resin composition, which is subjected to image exposure with the above light source, and then an organic solvent or a surfactant and an alkaline compound. An image can be formed on a substrate by development using an aqueous solution containing the solution. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Organic such as mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline Alkali compounds and the like. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples thereof include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent may be used alone or in a mixture with an aqueous solution.

  There are no particular limitations on the conditions for the development treatment, and usually the development temperature is in the range of 10 to 50 ° C., especially 15 to 45 ° C., particularly preferably 20 to 40 ° C. The development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.

(2-5) Thermosetting treatment method The color filter substrate after development is subjected to thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.

(2-6) Formation method of transparent electrode The color filter forms a transparent electrode such as ITO on the image as it is, and is used as a part of components such as a color display and a liquid crystal display device. In order to improve smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. In some cases, the transparent electrode may not be formed in applications such as a planar alignment type driving system (IPS mode).

[3] Spacer When the photosensitive resin composition of the present invention is used as a photosensitive resin composition for spacers, a photosensitive resin composition dissolved or dispersed in a solvent is usually applied onto a substrate on which a spacer is to be provided. When the film is supplied in a film shape or pattern by a method such as the above, and the solvent is dried and then supplied in a film shape, the pattern is formed by a method such as photolithography that performs exposure-development if necessary. Then, a spacer is formed on this board | substrate by performing a thermosetting process as needed.

(3-1) Supply Method to Substrate The photosensitive resin composition of the present invention is usually supplied onto the substrate in a state dissolved or dispersed in a solvent. As the supply method, a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method or the like can be used. Moreover, you may supply in pattern form by the inkjet method, the printing method, etc. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, there is no influence of mist adhering to the spin coating method, and the generation of foreign matter is suppressed. To preferred.

  The coating amount varies depending on the application. For example, in the case of a spacer, the dry film thickness is usually 0.5 μm or more, preferably 1 μm or more, usually 10 μm or less, preferably 8 μm or less, particularly preferably 5 μm or less. . In addition, it is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. When the variation is large, a nonuniformity defect occurs in the liquid crystal panel.

(3-2) Drying method Drying after supplying the photosensitive resin composition onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a reduced pressure chamber, without raising temperature. The drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected within a range of 15 seconds to 5 minutes at a temperature of 40 to 100 ° C., preferably at a temperature of 50 to 90 ° C., depending on the type of the solvent component, the performance of the dryer used, and the like. It is selected in the range of 30 seconds to 3 minutes.

(3-3) Exposure Method Exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive resin composition and irradiating an ultraviolet light source or a visible light source through this mask pattern. Further, a scanning exposure method using laser light may be used. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said exposure is not specifically limited. As the light source, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser, Examples thereof include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, blue-violet semiconductor laser, and near infrared semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

(3-4) Development Method After performing the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution containing an alkaline compound and a surfactant or an organic solvent. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Organic such as mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline Alkali compounds and the like. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples thereof include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent may be used alone or in combination with an aqueous solution.

(3-5) Thermosetting treatment method The substrate after development is preferably subjected to thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes.

[4] Ribs (Liquid crystal alignment protrusions)
Ribs (liquid crystal split alignment protrusions) are protrusions formed on a transparent electrode in order to improve the viewing angle of a liquid crystal display device, and the liquid crystal is locally tilted by using the slope of the protrusions within one pixel. The liquid crystal is divided in multiple directions. Hereinafter, a method for forming the rib will be described in detail.

(4-1) Application and development method The present invention is provided on a transparent substrate usually having a thickness of 0.1 to 2 mm on which a black matrix and red, blue and green color filters are provided, and further 150 nm of ITO is deposited thereon. The photosensitive resin composition is applied using an application device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, or a spray. The coating film thickness of the composition is usually 0.5 to 5 μm. After the coating film made of the composition is dried, a photomask is placed on the dried coating film, and image exposure is performed through the photomask. After exposure, an unexposed uncured portion is removed by development to form a pixel. Usually, an image obtained after development is required to have a fine line reproducibility with a width of 5 to 20 μm, and there is a tendency that a finer fine line reproducibility is required due to a demand for a high-quality display. In order to stably reproduce high-definition fine lines, the cross-sectional shape of the fine line image after development is a rectangular shape with a clear contrast between the non-image and the image area. A wide development margin is preferable.

(4-2) Heating method In the present invention, the developed image has a cross-sectional shape close to a rectangular shape. In order to obtain an arched shape necessary for the rib shape, it is usually 150 ° C. or higher, preferably 180 ° C. or higher, more preferably 200 ° C. or higher, usually 400 ° C. or lower, preferably 300 ° C. or lower, more preferably 280 ° C. or lower. And a heat treatment of 10 minutes or more, preferably 15 minutes or more, more preferably 20 minutes or more, usually 120 minutes or less, preferably 60 minutes or less, more preferably 40 minutes or less, and a rectangular cross-sectional shape. Is deformed into an arch shape to form ribs having a width of 0.5 to 20 μm and a height of 0.2 to 5 μm. As the range of deformation during heating, the photosensitive resin composition and heating conditions are adjusted as appropriate, and the contact angle (W1) formed from the side surface of the thin line image (rectangular image cross-sectional shape) before heating and the substrate plane is the above heating. When the contact angle (W2) formed from the side surface of the thin line image after processing and the substrate plane is compared, W1 / W2 is 1.2 or more, preferably 1.3 or more, more preferably 1.5 or more, usually 10 Hereinafter, it is preferably 8 or less. The higher the heating temperature or the longer the heating time, the higher the deformation rate. Conversely, the lower the heating temperature or the shorter the heating time, the lower the deformation rate.

[Liquid Crystal Display]
A liquid crystal display device usually forms an alignment film on a color filter, spreads spacers on the alignment film, and then bonds to a counter substrate to form a liquid crystal cell, injects liquid crystal into the formed liquid crystal cell, Complete by connecting to the counter electrode. As the alignment film, a resin film such as polyimide is suitable. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.

  As the spacer, a spacer having a size corresponding to the gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. As described above, a photo spacer (PS) of a transparent resin film is formed on the color filter substrate by photolithography, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

  The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of reduced pressure in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The warming hold during decompression is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like are known, but any of them may be used.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further more concretely, the scope of the present invention is not limited to these Examples.

[Compound represented by the above formula (1) and comparative compound]
As the compound represented by the above formula (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%.

<Method for Synthesizing 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%.

[Alkali-soluble unsaturated resin]
The alkali-soluble unsaturated resin is synthesized by the following synthesis method.
<Synthesis Example 1>
A nitrogen gas purge was applied to a flask equipped with a stirrer, a thermometer, and a condenser tube, and then 100.0 g of 5,5 ′-(1-methylethylidene) bis [2-cyclohexylphenol] (the following formula (5)) And 700.0 g of epichlorohydrin were added and dissolved. Further, the mixture was heated to 65 ° C., 11.0 g of sodium hydroxide was added in portions over 90 minutes, and then further reacted at 65 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, epichlorohydrin was distilled off at 130 ° C., and washing with water was repeated three times to obtain an epoxy compound represented by the following formula (6). The obtained epoxy compound was white powder, and the epoxy equivalent was 257 g / eq.

  100.0 g of the obtained epoxy compound, 29.0 g of acrylic acid, 0.06 g of p-methoxyphenol, 2.6 g of triphenylphosphine, and 126.0 g of propylene glycol monomethyl ether acetate were charged into a reaction vessel, and the mixture was kept at 120 ° C. for 2 hours. Further, the mixture was stirred at 95 ° C. until the acid value became 5 mg-KOH / g or less. It took 10 hours for the acid value to reach the target (acid value 4.0).

<Synthesis Method of Alkali-Soluble Unsaturated Resin (AI) Solution>
To 257 parts of the reaction solution obtained in Synthesis Example 1, 60 parts of propylene glycol monomethyl ether acetate is added, 10.7 parts of hexamethylene diisocyanate is added and reacted at 90 ° C. for 3 hours, and trimellitic anhydride 28.5 is added. Then, an alkali-soluble unsaturated resin (AI) solution having an acid value of 96 and a weight average molecular weight of 2580 in terms of polystyrene measured by GPC was obtained.

<Method for synthesizing alkali-soluble unsaturated resin (A-II) solution>
To 80 parts of the reaction solution obtained in Synthesis Example 1, 15 parts of propylene glycol monomethyl ether acetate is added, 9.6 parts of biphenyltetracarboxylic dianhydride is added, and the mixture is reacted at 120 ° C. for 2 hours. Further, tetrahydrophthalic anhydride is added. 5 parts was added and reacted at 95 ° C. for 3 hours to obtain an alkali-soluble unsaturated resin (A-II) solution having an acid value of 106 and a polystyrene-equivalent weight average molecular weight of 3700 measured by GPC.

<Synthesis Method of Alkali Soluble Unsaturated Resin (A-III) Solution>
Bisphenol A type epoxy compound (following formula (7), epoxy equivalent 186 g / eq) 100 parts, acrylic acid 40 parts, p-methoxyphenol 0.06 parts, triphenylphosphine 2.4 parts, propylene glycol monomethyl ether acetate 126 parts Was stirred at 95 ° C. until the acid value was 5 mg-KOH / g or less. It took 10 hours for the acid value to reach the target (acid value 1.0). Next, 40 parts of propylene glycol monomethyl ether acetate was added to the resulting reaction solution, 19.5 parts of isophorone diisocyanate was added, reacted at 90 ° C. for 3 hours, and 39.3 parts of trimellitic anhydride were further added. The mixture was reacted at 90 ° C. for 3 hours to obtain an alkali-soluble unsaturated resin (A-III) solution having an acid value of 113 and a weight-average molecular weight of 2400 in terms of polystyrene measured by GPC.

<Method for synthesizing alkali-soluble unsaturated resin (A-IV) solution>
Bisphenol A type epoxy compound (formula (7), epoxy equivalent 186 g / eq) 100 parts, acrylic acid 40 parts, p-methoxyphenol 0.06 parts, triphenylphosphine 2.4 parts, propylene glycol monomethyl ether acetate 126 parts Was stirred at 95 ° C. until the acid value was 5 mg-KOH / g or less. It took 10 hours for the acid value to reach the target (acid value 1.0). Next, 40 parts of propylene glycol monomethyl ether acetate was added to the obtained reaction liquid, 17.5 parts of isophorone diisocyanate was added, and the mixture was reacted at 90 ° C. for 3 hours, and 46.8 parts of trimellitic anhydride was further added. The mixture was reacted at 90 ° C. for 3 hours to obtain an alkali-soluble unsaturated resin (A-IV) solution having an acid value of 136 and a weight average molecular weight of 2840 in terms of polystyrene measured by GPC.

<Preparation of photosensitive resin composition>
[Example 1]
In a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 60.0 g (30.0 g in terms of solid content) of an alkali-soluble unsaturated resin (AI) solution and 10.0 g of dipentaerythritol hexaacrylate “CGI-242” (manufactured by Ciba Specialty Chemicals Co., Ltd., structural formula is as follows) 4.0 g and the product name “Disperbyk182” manufactured by Big Chemie Japan Co., Ltd. as a urethane-based nitrogen atom-containing polymer dispersant. 224.0 g of carbon black dispersion solution (56.0 g in terms of solid content, including 43.0 g of carbon black and 13.0 g of polymer dispersant) was added to 218.0 g of propylene glycol monomethyl ether acetate, Further, the above compound 1 was added so as to be 3% by mass in the solid content, and was kept at room temperature all day and night. After 拌溶 solution was prepared filter filtered photosensitive resin composition.

[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 instead of the compound 1, respectively.

[Example 21]
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the alkali-soluble unsaturated resin (A-III) solution was used instead of the alkali-soluble unsaturated resin (AI) solution.

[Example 22]
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the alkali-soluble unsaturated resin (A-IV) solution was used instead of the alkali-soluble unsaturated resin (AI) solution.

[Example 23]
A photosensitive resin composition was prepared in the same manner as in Example 3, except that the alkali-soluble unsaturated resin (A-III) solution was used instead of the alkali-soluble unsaturated resin (AI) solution.

[Example 24]
A photosensitive resin composition was prepared in the same manner as in Example 3, except that the alkali-soluble unsaturated resin (A-IV) solution was used instead of the alkali-soluble unsaturated resin (AI) solution.

[Comparative Examples 1-8]
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the comparative compounds 1 to 8 were used instead of the compound 1, respectively.

[Comparative Examples 9 to 11]
Comparative Example 7 except that the alkali-soluble unsaturated resin (A-II), (A-III) and (A-IV) solutions were used instead of the alkali-soluble unsaturated resin (A-1) solution, respectively. In the same manner, a photosensitive resin composition was prepared.

[Evaluation]
The photosensitive resin compositions of Examples 1 to 24 and Comparative Examples 1 to 11 were spin-coated on a 6 inch silicon substrate and then dried to form a 5.0 ± 1.0 μm coating film. Next, using a mirror projection aligner (product name: MPA-600FA, manufactured by Canon Inc.), the coating film was irradiated with ultraviolet rays through a negative mask on which a line pattern of 5 to 40 μm was formed. The exposure amount was 100 mJ / cm ² . Next, after being left in a light shielding box for 1 hour, it was heated on a hot plate at 120 ° C. for 60 seconds. Then, using a 2.38 mass% tetramethylammonium hydroxide aqueous solution, paddle development is performed for 1.2 times the development time required to remove the unexposed portions, rinsed with water, and then dried. Thus, a line pattern for pattern adhesion evaluation was formed.
And the formed line pattern was observed with the scanning electron microscope (SEM), and pattern adhesiveness was evaluated. The pattern adhesion was evaluated as “good” when the 5 μm line was completely reproduced, and as “bad” when completely peeled off, partially peeled off, or chipped.

Similarly, the coating film was irradiated with ultraviolet rays through a negative mask having a line pattern of 5 to 40 μm. The exposure amount was 100 mJ / cm ² . Next, a line pattern for evaluating pattern straightness was formed by the same process as that for forming a line pattern for evaluating pattern adhesion.
And the formed line pattern was observed with the scanning electron microscope (SEM), 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.
Furthermore, the presence or absence of a residue in the unexposed part after development was evaluated.
The results are shown in Tables 1 and 2 below.

  As can be seen from Table 1, when the photosensitive resin compositions of Examples 1 to 24 to which the compounds 1 to 20 represented by the above formula (1) were added were used, a 5 μm line pattern adhered to the substrate. Moreover, the straightness of the line pattern was also excellent. Further, when the photosensitive resin compositions of Examples 1 to 24 were used, no development residue was present.

  On the other hand, as can be seen from Table 2, when the photosensitive resin compositions of Comparative Examples 1 to 11 in which the compound represented by the above formula (1) was not added, pattern adhesion, pattern All of the straight running properties were inferior to those of Examples 1 to 24, and good micropatterning characteristics were not obtained.

Claims (11)

A photosensitive resin composition comprising an organic binder and a compound represented by the following formula (1), wherein the organic binder has at least two epoxy groups in the molecule (a): A photosensitive resin composition comprising an alkali-soluble unsaturated resin which is an adduct of an isocyanate compound (c) as a reaction product of a carboxylic acid (b) with an unsaturated group.

(In the formula (1), ^{R 1} and ^{R 2} each independently represent a hydrogen atom or an organic group. However, .R ¹ and ^{R 2} represents an organic group at least one of the ^{R 1} and ^{R 2,} which There may also be bonded together to form a ring structure, optionally .R ³ also contain binding heteroatoms, .R ⁴ and R ⁵ represents a single binding 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, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group or .R ⁶ in which an organic group, , R ⁷ , R ⁸ , and R ⁹ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group Shows a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group, or an organic group. However, never R ⁶ and R ⁷ is a hydroxyl group .R ^6, R ⁷ , R ⁸ , and R ⁹ may be bonded to each other to form a cyclic structure, and may include a heteroatom bond, and R ¹⁰ may be a hydrogen atom or an organic group. Show.) The photosensitive resin composition of Claim 1 in which the epoxy compound (a) which has an at least 2 or more epoxy group in the said molecule | numerator contains the compound represented by a following formula (Ia).

[In the formula (Ia), X is represented by the following formula (II).

(Wherein ^(II), R 11 ^{to R 26} each independently represent a hydrogen atom, an alkyl group, or may have a substituent phenyl group having 1 to 12 carbon ^{atoms, R 11} and R ¹² , when R ¹³ and R ¹⁴ are both alkyl groups, they may be linked to each other to form a ring. N is 0 or 1)] A photosensitive resin composition containing an organic binder and a compound represented by the following formula (1), wherein the organic binder contains a phenolic hydroxyl group having at least two phenolic hydroxyl groups in the molecule A photosensitive resin composition comprising an alkali-soluble unsaturated resin which is an adduct of an isocyanate compound (c) as a reaction product of a compound (f) and an unsaturated group-containing epoxy compound (g).

(In the formula (1), ^{R 1} and ^{R 2} each independently represent a hydrogen atom or an organic group. However, .R ¹ and ^{R 2} represents an organic group at least one of the ^{R 1} and ^{R 2,} which ^May be bonded to each other to form a cyclic structure and may contain a heteroatom bond, R ³ represents a single bond, R ⁴ and R ⁵ each independently represents a hydrogen atom, a halogen atom, R ⁶ represents a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group . R ⁷ , R ⁸ , and R ⁹ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group Shows a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group, or an organic group. However, never R ⁶ and R ⁷ is a hydroxyl group .R ^6, R ⁷ , R ⁸ , and R ⁹ may be bonded to each other to form a cyclic structure, and may include a heteroatom bond, and R ¹⁰ may be a hydrogen atom or an organic group. Show.) The photosensitive resin composition of Claim 3 in which the phenolic hydroxyl group containing compound (f) which has at least 2 or more phenolic hydroxyl group in the said molecule | numerator contains the compound represented by a following formula (If).

[In the formula (If), X is represented by the following formula (II).

(Wherein ^(II), R 11 ^{to R 26} each independently represent a hydrogen atom, an alkyl group, or may have a substituent phenyl group having 1 to 12 carbon ^{atoms, R 11} and R ¹² , when R ¹³ and R ¹⁴ are both alkyl groups, they may be linked to each other to form a ring. N is 0 or 1)] The isocyanate DOO of compound (c) is a photosensitive resin composition according to any of claims 1 which is a compound having two or more in a molecule an isocyanate group 4. The photosensitive resin composition according to claim 2 or 4, wherein X in the formula (Ia) or the formula (If) is represented by any one of the following formulas (IIA), (IIB), and (IIC). .

(In the formulas (IIA), (IIB), and (IIC), R ^{11 to} R ²⁶ and n have the same meanings as in the formula (II).) The photosensitive resin composition according to claim 6, wherein the formula (IIA) is represented by the following formula (IIAa) or (IIAb).

(In the formulas (IIAa) and (IIAb), R ¹¹ and R ¹² have the same meanings as in the formula (II).)   The photosensitive resin composition in any one of Claim 1 to 7 containing a photoinitiator.   The photosensitive resin composition in any one of Claim 1 to 8 containing a coloring agent.   A color filter formed using the photosensitive resin composition according to claim 1. A liquid crystal display device having a member formed using the photosensitive resin composition according to claim 1.