JP4839710B2 - Photosensitive resin composition, color filter, and liquid crystal display device - Google Patents

Abstract

A photosensitive resin composition comprising an alkali-soluble unsaturated resin as an organic binder produced by reacting an epoxy compound (a) having two or more epoxy groups in its molecule with an unsaturated group-containing carboxylic acid (b)and further reacting the reaction product with an isocyanate group-containing compound (c). A photosensitive resin composition comprising an alkali-soluble unsaturated resin produced by reacting a phenolic hydroxyl group-containing compound (f) having two or more phenolic hydroxyl groups in its molecule with an unsaturated group-containing epoxy compound (g) and further reacting the reaction product with an isocyanate group-containing compound (c).

Description

  The present invention relates to a photosensitive resin composition suitable for image formation, black matrix use, overcoat use, rib use, and spacer use for color filters used in liquid crystal panels such as liquid crystal displays, and the photosensitive resin composition. The present invention relates to a color filter and a liquid crystal display device using the same.

  Conventionally, 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 Things (resists) have been used. Various compositions have been proposed for color filter resists from the viewpoint of developability, pattern accuracy, adhesion, etc. As one of them, for the purpose of shortening the processing time in the forming process and improving the yield, As the resin contained in the resin composition, an unsaturated group-containing resin obtained by further reacting a reaction product of an epoxy resin with an unsaturated group-containing carboxylic acid or its anhydride with a polybasic carboxylic acid or its anhydride is used. Have been disclosed (Patent Documents 1 to 3).

On the other hand, various resin compositions are also disclosed in the paint field. For example, a resin comprising a reaction product of a compound having two isocyanate groups in a compound molecule having a pendant group and a divalent reactive group. It discloses about the composition using this (patent document 4). However, diverting the resin composition as such a coating to a resist that requires an operation such as development and is expected to have fine processing accuracy at that time has different purposes and has applicability and effects. Since it cannot be predicted by those skilled in the art, such a resin composition for paints has not been used for resists for color filters.
JP 2001-174621 A Japanese Patent No. 2878486 Japanese Patent Laid-Open No. 10-168033 USP 5109097

  However, the above-mentioned resist used in conventional liquid crystal panels or the like reacts a polybasic carboxylic acid or its anhydride with a structural unit consisting of a reaction product of an epoxy resin and an unsaturated group-containing carboxylic acid or its anhydride. If the ester part is cleaved during storage because of the ester formed, the resin properties such as viscosity, development speed, etc. due to changes in molecular weight due to ester crosslinking, and consequently resist properties. A significant change occurred, causing troubles in the coating process and the image forming process, and thus had a large practical problem.

In addition, in the photosensitive resin composition containing the above-described photosensitive colored resin composition and containing a photopolymerizable component, a photopolymerization initiator, and a binder resin, the steps of coating, drying, exposure, and development are generally performed. In order to be subjected to an optical lithography process,
(1) Residues and background stains do not occur in the removed part in the development process. (2) The removed part has sufficient solubility. (3) It is always possible to improve the pixel formability such as the sharpness of the pattern edge. Although required, when a pixel is formed using a photosensitive colored resin composition having a high content of the colorant as described above,
(1) Residues and background stains occur on the unexposed area of the substrate in the development process. (2) Inferior sharpness of the edge shape of the pixel due to poor solubility in the unexposed area. 3) A phenomenon that the sensitivity of the pixels formed in the exposed portion 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.
In other words, even if it is sufficiently cured on the light-irradiated surface side, it should not be cured on the base surface side. (3) Since a large amount of black color material insoluble in the developer is added, it is good that the developability is remarkably reduced. Is a hindrance in imparting a good photosensitive property.

  The present invention solves the above-mentioned conventional problems, has good adhesion to the substrate, and even when containing a coloring material such as pigment or carbon black at a high concentration, a photospacer that does not require a pigment or the like Even in the case of ribs, it has an excellent balance between sensitivity and solubility, sharpness of pixel edge shape and taper shape, adhesion, surface smoothness, antifouling property, heat resistance, and storage stability. It aims at providing the photosensitive resin composition which is excellent in this.

  Another object of the present invention is to provide a high-quality color filter and further a high-quality liquid crystal display device using such a photosensitive resin composition.

  As a result of intensive studies, the present inventors have determined that a reaction product of an epoxy compound (a) having a specific structure as a binder resin and an unsaturated group-containing carboxylic acid (b), and a compound (c) further having an isocyanate group When an alkali-soluble unsaturated resin having a specific acid value obtained by reacting is used, it has an excellent balance between sensitivity and solubility, and further, sharpness, adhesion and surface smoothness of pixel edge shape and taper shape. The inventors have found that it is possible to realize a photosensitive resin composition that is excellent in various performances such as antifouling property and heat resistance, and also excellent in storage stability, and has reached the present invention.

The photosensitive resin composition of the present invention (Claim 1) is a photosensitive resin composition containing an organic binder, and the organic binder has an epoxy compound having at least two epoxy groups in the molecule. and (a), the reaction product of an unsaturated group-containing carboxylic acid (b), further containing an alkali-soluble unsaturated resin obtained by reacting a compound having an isocyanate group (c), at least in the molecule The epoxy compound (a) having two or more epoxy groups includes a compound represented by the following general formula (Ia), and the following general formula (II) is represented by the following general formula (IIAa) or (IIAb) characterized in that that.

(In the above general formulas (IIAa) and (IIAb), R ¹ , R ² Is as defined in the general formula (II). )

The photosensitive resin composition according to claim 2 is a photosensitive resin composition containing an organic binder, wherein the organic binder has at least two phenolic hydroxyl groups in the molecule. and (f), the reaction product of an unsaturated group-containing epoxy compound (g), further containing an alkali-soluble unsaturated resin obtained by reacting a compound having an isocyanate group (c), at least in the molecule The phenolic hydroxyl group-containing compound (f) having two or more phenolic hydroxyl groups includes a compound represented by the following general formula (If), and the following general formula (II) is represented by the following general formula (IIAa) or (IIAb) ) .

(In the above general formulas (IIAa) and (IIAb), R ¹ , R ² Is as defined in the general formula (II). )

The photosensitive resin composition according to claim 3, in claim 1 or 2, wherein the compound having an isocyanate group (c) is a compound having two or more in a molecule an isocyanate group.

The photosensitive resin composition according to claim 4 is characterized in that in any one of claims 1 to 3 , it further contains a photopolymerization initiator.

The photosensitive resin composition according to claim 5 is characterized in that it further contains a color material in any one of claims 1 to 4 .

The color filter of the present invention (Claim 6 ) is formed using the photosensitive resin composition of the present invention.

The liquid crystal display device of the present invention (invention 7 ) has a member formed by using the photosensitive resin composition of the present invention, for example, a color filter, a spacer, a rib material and the like.

  According to the present invention, the adhesiveness with the substrate is good, and even when containing a coloring material such as pigment or carbon black at a high concentration, especially in the case of a photo spacer or rib that does not require a pigment or the like, the sensitivity and Provided is a photosensitive colored resin composition that has excellent solubility balance, and further has excellent pixel edge shape and taper shape sharpness, adhesion, surface smoothness, antifouling property, heat resistance, and storage stability. The And using such a photosensitive resin composition, a high quality color filter and also a high quality liquid crystal display device can be provided.

  Hereinafter, embodiments of the present invention will be described in detail. In addition, the following description is an example of the embodiment of this invention, and this invention is not specified to these, unless the summary is exceeded.

[Photosensitive resin composition]
<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.

(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 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 represented by R ^{1 to} R ¹⁶ may be a linear alkyl group, a branched alkyl group, or 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 ¹ and R ² and R ³ and R ⁴ include a cycloalkane ring having 5 to 15 carbon atoms or an adamantane ring. In addition, the ring formed by connecting R ¹ and R ² , R ³ and R ⁴ may have an arbitrary number of substituents at an arbitrary position. 5 alkyl groups.

（上記一般式（IIＡ）〜（IIＣ）において、Ｒ^１〜Ｒ¹⁶及びｎは前記一般式（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 ^{1 to} R ¹⁶ and n have the same meaning as in the general formula (II).)

（式中、Ｒ^１，Ｒ^２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).

(Wherein R ¹ and R ² 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.

  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.

（上記一般式（IIＤ），（IIＥ）において、Ｒ^１，Ｒ^２は前記一般式（II）におけると同義であり、Ｒ¹⁷〜Ｒ²⁴はそれぞれ独立に、水素原子又は置換基を有していても良い炭素数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 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)”). Or 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 the general formulas (IID) and (IIE), R ¹ and R ² have the same meanings as in the general formula (II), and R ^{17 to} R ²⁴ each independently have a hydrogen atom or a substituent. It represents an alkyl group having 1 to 3 carbon atoms.)

（上記一般式（IIＤａ）において、Ｒ^１，Ｒ^２は前記一般式（II）におけると同義であり、Ｒ¹⁷，Ｒ²¹はそれぞれ独立に、水素原子又は置換基を有していても良い炭素数１〜３のアルキル基を示す。） Moreover, in the said epoxy compound (a-2), the compound by which X is represented with the following general formula (IIDa) is especially preferable.

(In the general formula (IIDa), R ¹ and R ² have the same meanings as in the general formula (II), and R ¹⁷ and R ²¹ are each independently a carbon atom optionally having a hydrogen atom or a substituent. Represents an alkyl group of 1 to 3)

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

Examples of the epoxy compound represented by the general formula (Ia) include a compound represented by the following general formula (IV) and an epihalohydrin such as epichlorohydrin and epibromohydrin, sodium hydroxide, potassium hydroxide, and 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 which 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 off 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. A solid or aqueous solution of an alkali metal hydroxide is added to the halohydrin etherified product of the compound represented by the general formula (IV) obtained by reacting for 1 to 5 hours, 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 the general 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 weight or more, preferably 4% by weight or more, and usually 20% by weight or less, preferably 15% by weight or less based on the amount of epihalohydrin. When an aprotic polar solvent is used, the amount used is usually 5% by weight or more, preferably 10% by weight or more, and usually 100% by weight or less, preferably 90% by weight or less based on the amount of epihalohydrin.

  After the epoxidation reaction product is washed with water or without washing, epihalohydrin and other added solvents are removed at 110 to 250 ° C. under a pressure of 1.3 kPa (10 mmHg) under reduced pressure. In addition, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is dissolved again 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 generated salt is removed by filtration, washing with water, and the like, 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 a bisphenol A type epoxy resin (for example, an oiled 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 (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) Or a compound represented by Examples thereof include copolymers obtained by reacting one or two or more selected with each other (in this specification, “(meth) acrylate”, “(meth) acryl˜”, etc. are “acrylate”). Or, “methacrylate”, “acrylic or methacrylic”, etc., for example, “(meth) acrylic acid” described later means “acrylic acid or methacrylic acid”).

（式中、Ｒ²¹は水素又はエチル基、Ｒ²²は水素又は炭素数１〜６のアルキル基を示し、ｒは２〜１０の整数である。）

(Wherein R ²¹ represents hydrogen or an ethyl group, R ²² represents hydrogen 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 weight or more, particularly preferably 20% by weight or more, preferably 70% by weight with respect to the second component of the copolymerization type epoxy resin. % Or less, particularly preferably 50% by weight 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 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 acids 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 tetrahydrophthal 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acryloyloxybutyladipic acid, 2 -(Meth) acryloyloxybutyl hydrophthalic acid, 2- (meth) acryloyloxybutyl phthalic acid, 2- (meth) acryloyloxybutylmaleic acid (meth), acrylic acid with ε-caprolactone, β-propio Monomers formed by adding lactones such as lactone, γ-butyrolactone, and δ-valerolactone, (meth) acrylic acid dimer, compounds formed by reaction of pentaerythritol tri (meth) acrylate with succinic anhydride Alternatively, it is formed by the reaction of pentaerythritol tri (meth) acrylate and phthalic anhydride. Things and the like.

  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 weight or more, particularly preferably 0.3% by weight, based on the reaction raw material mixture (total of epoxy compound (a) and unsaturated group-containing carboxylic acid (b)). Above, it is preferably 10% by weight or less, particularly preferably 5% by weight 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 weight% or more with respect to a reaction raw material mixture, Most preferably, it is 0.1 weight% or more, Preferably it is 10 weight% or less, Most preferably, it is 5 weight%.

  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 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. .

(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 according to the present invention includes a polybasic acid anhydride (d) added to an isocyanate compound (c) adduct of a reaction product of the epoxy compound (a) and the unsaturated group-containing carboxylic acid (b). After addition of, 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 ").

(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 general formula (If), X has the same meaning as X in the general formula (Ia), and the preferred structure thereof is also 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 weight or more, particularly preferably 0.1% by weight 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 weight or more, preferably 10% by weight or less, particularly preferably 5% by weight 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 weight% or more with respect to a reaction raw material mixture, Most preferably, it is 0.1 weight% or more, Preferably it is 10 weight% or less, Most preferably, it is 5 weight%.

  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 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 weight average molecular weight (Mw) measured by GPC of the alkali-soluble unsaturated resin according to 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. is there. If the weight 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.

  Moreover, the acid value (mg-KOH / g) of the alkali-soluble unsaturated resin according to 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 Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 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 monofuryl-1,3,4 -Halomethylated oxadi, such as oxadiazole Sol derivative; 2- (2′-chlorophenyl) -4,5-diphenylimidazolol dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl)- Imidazole derivatives such as 4,5-diphenylimidazole dimer; Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t- Anthraquinone derivatives such as butylanthraquinone and 1-chloroanthraquinone; benzophenone, Michler's ketone, 2 Benzophenone derivatives such as methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 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) Acetophenone derivatives such as ketones, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethyl Thioxanthone, 2-isopropylthioxan , Thioxanthone derivatives such as 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; benzoic acid such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate Ester derivatives; 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, dicyclopentadienyl-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-difluorophenyl -1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluoropheny Titanocene derivatives such as 1-yl, dicyclopentagenyl-Ti-2,6-difluoro-3- (pyr-1-yl) -phen-1-yl. Further, 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 preferable. As a polymer dispersant,
[1] Urethane dispersant [2] Graft copolymer containing nitrogen atom [3] A block consisting of an A block having a quaternary ammonium base in the side chain and a 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 may mix and use 2 or more types.

  In the present invention, these nitrogen atom-containing dispersants and the specific alkali-soluble unsaturated resin according to the present invention are used in combination to form a photosensitive colored resin composition while maintaining dispersion stability. It is possible to achieve high adhesion at the time of development between the coated film and the substrate and to suppress the remaining undissolved material.

  The form of the nitrogen atom in the nitrogen atom-containing dispersant is preferably an amino group or a quaternary ammonium salt. This is because these functional groups usually have basicity so that they can easily coordinate with acidic groups such as pigments and pigment derivatives, thereby contributing 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, the voltage holding ratio of the liquid crystal is lowered when used in a liquid crystal display device, 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) a polyisocyanate compound,
Examples of the polyisocyanate compound 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'-tetramethyl Aliphatic diisocyanate having an aromatic ring such as silylene 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. 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 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 weight or more, preferably 20 parts by weight or more, more preferably, a compound having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. 30 parts by weight or more, usually 200 parts by weight or less, preferably 190 parts by weight or less, more preferably 180 parts by weight or less, and the compound having an active hydrogen and a tertiary amino group in the same molecule is usually 0.2 parts by weight or more, Preferably it is 0.3 parts by weight or more, usually 25 parts by weight or less, preferably 24 parts by weight or less.

  The polystyrene-reduced weight 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.

  Manufacture of the urethane type dispersion resin which concerns on this invention is performed in accordance with the well-known method of polyurethane resin manufacture. 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 (Ia) or / and a repeating unit represented by the following general formula (ii).

（上記一般式（Ｉ−ａ），（ii）中、Ｒ³¹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。

（上記一般式（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。）

（上記一般式（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−Ｒ³²（Ｒ³²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。）

（上記一般式（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 above general formulas (Ia) and (ii), R ³¹ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably 2 to 2 carbon atoms. 3 is more preferably an ethylene group, and A represents a hydrogen atom or any one of the following general formulas (iii) to (v), preferably the following general formula (iii).

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

(In the above 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 having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy. W ² represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene, butylene, etc. Among them, an alkylene group having 2 to 3 carbon atoms such as ethylene or propylene is preferable. ² represents a hydrogen atom or —CO—R ³² (R ³² represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, and hexyl; 5 is preferable.) Q represents an integer of 1 to 20, and preferably an integer of 5 to 10.)

(In the 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, alkyl having 10 to 20 carbon atoms such as stearyl. And a C10-20 hydroxyalkyl group having 1 to 2 hydroxyl groups such as a monohydroxystearyl group)))

The content of the repeating unit represented by the general formula (Ia) or (ii) in the graft copolymer according to the present invention is preferably higher, and is generally 50 mol% or more in total, preferably 70 mol. % Or more. The repeating unit represented by the general formula (Ia) and the repeating unit represented by the general formula (ii) may both be present, and the content ratio is not particularly limited, It is preferable to contain more repeating units of the formula (Ia). The total number of repeating units represented by formula (Ia) or (ii) in the graft copolymer is 1 or more, preferably 10 or more, more preferably 20 or more, and usually 100 or less, preferably Is 70 or less, more preferably 50 or less. Further, the graft copolymer may contain a repeating unit other than the general formula (Ia) and the general formula (ii). Examples of the other repeating unit include an alkylene group and an alkyleneoxy group. it can. The graft copolymer according to the present invention preferably has —NH ₂ and —R ³¹ —NH ₂ (R ³¹ is as defined in formulas (Ia) 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. When the weight average molecular weight is less than 3,000, the color material cannot be aggregated, and the viscosity may be increased or gelled. When the weight average molecular weight 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 Represents an atom or a cyclic or chain hydrocarbon group which may be substituted, or two or more of R ^1a , R ^2a and R ^3a may be bonded to each other to form a cyclic structure; .Y ^- has a quaternary ammonium salt represented by represents) a counter anion.. 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.

（上記式中、ＲはＲ^1a〜Ｒ^3aのうち何れかの基を表す。）

(In the above formula, R represents any group 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 a may have a substituent an alkyl group having 1 to 3 carbon atoms, or 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.

（上記一般式（１）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良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良い。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 the general formula (1), 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 (1), 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 represents 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 ⁻ and PF ₆ ⁻ .

  The partial structure containing the specific quaternary ammonium base as described above may be contained in one or more A blocks. 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. In addition, a partial structure not containing the 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 weight, more preferably 0 to 20% by weight. Most preferably, it is not included in the A block.

  On the other hand, as the B block constituting the block copolymer of the dispersant, for example, styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, (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- Dimethylaminoethyl acrylic Vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether, (meth) acrylamide monomers such as amide N- methacryloyl morpholine, polymer structure obtained by copolymerizing comonomers such.

  The B block is preferably a partial structure derived from a (meth) acrylic acid ester monomer represented by the following general formula (2).

（上記一般式（２）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良い環状又は鎖状のアルキル基、置換基を有していても良いアリル基、又は置換基を有していても良いアラルキル基を表す。）

(In the above general formula (2), 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 a good allyl group or an aralkyl group which may have a substituent.)

  Two or more kinds of partial structures 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 monomers is present in a B block that does not contain a quaternary ammonium base, each partial structure is contained in the B block in any form of random copolymerization or block copolymerization. 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 weight, more preferably 0 to 20% by weight, but it is most preferable that a partial structure other than the (meth) acrylate monomer is not contained 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.

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

  In synthesizing such a dispersant, JP-A-9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews et al, Macromolecules. , 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Right hand, Koichi Hatada, Polymer processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Inoue. The publicly known methods described in Shohei, Synthetic Organic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987) can be employed.

  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 (weight 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 A weight average in terms of polystyrene is usually preferably in the range of 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 polyester, such as polyester, such as polycaprolactone, and polyethyleneglycol, for example is mentioned. 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 (3).

  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, Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to 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 A silane coupling agent can be added to improve adhesion to the substrate. 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 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.

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

  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 blending amount of the alkali-soluble unsaturated resin is usually 10% by weight or more, preferably 20% by weight or more, and usually 80% by weight or less, preferably 70%, based on the total solid content of the photosensitive resin composition of the present invention. % By weight or less. 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 weight or more, preferably 10% by weight. The above is usually in the range of 500% by weight or less, preferably 200% by weight 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, “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 weight or more and 90% by weight or less. .

  When blending a photopolymerization initiator, the content thereof is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably, based on the total solid content of the photosensitive resin composition of the present invention. It is 0.7% or more, usually 30% by weight or less, preferably 20% by weight 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 to 70 weight% with respect to the total amount of solids in the photosensitive colored resin composition of this invention. In this range, 10 to 70% by weight is more preferable, and 20% by weight or more and 60% by weight 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 when the liquid crystal cell is formed. On the other hand, if the content of the color material is too large, sufficient image formability may not be obtained.

  In the case of blending a dispersant, among the nitrogen atom-containing dispersants, when the [1] urethane-based dispersion resin is used, the content relative to the color material component in the photosensitive colored resin composition is usually 10 wt. % Or more, preferably 20% by weight or more, particularly preferably 30% by weight or more, and usually 300% by weight or less, preferably 100% by weight or less, particularly preferably 80% by weight 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 with respect to the color material component in the photosensitive colored resin composition is usually 10% by weight or more, preferably 20% by weight or more, particularly preferably. It is 30% by weight or more, usually 300% by weight or less, preferably 100% by weight or less, particularly preferably 80% by weight 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.

  Further, when the [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 weight or more, preferably 20% by weight or more, and particularly preferably. It is 30% by weight or more, usually 300% by weight or less, preferably 100% by weight or less, particularly preferably 80% by weight 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.

  Further, the phosphate ester type dispersant is usually 5 parts by weight or more, preferably 10 parts by weight or more, and usually 100 parts by weight or less, preferably 80 parts, per 100 parts by weight of the [3] block copolymer. It is preferable to use it in parts by weight 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 thereof is usually 90% by weight or less, preferably 80% by weight or less, based on the total solid content of the photosensitive resin composition of the present invention. 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 weight% or more normally, Preferably it is 5 weight% 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 of a color filter used for a liquid crystal panel such as a liquid crystal display, a black matrix, an overcoat, a rib, and a spacer. 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 materials 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, and 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, to improve surface properties such as adhesion, corona discharge treatment, ozone treatment, silane coupling agents, thin film formation treatment of various resins such as 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, etc. are 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 the 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, black color material such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black or the like, or 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 The photosensitive colored resin composition for the color filter can be coated 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. In particular, the die coating method significantly reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. To preferred.

  If the thickness of the coating film is too thick, pattern development becomes difficult, and it may be difficult to adjust the gap in the liquid crystal cell forming process. 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 a 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 solvent component and the performance of the dryer used. 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. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a 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 Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. 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 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) Transparent electrode formation method The color filter is used as a part of components such as a color display and a liquid crystal display by forming a transparent electrode such as ITO on the image as it is. In order to improve smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

[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 the form of a film by a method such as the above, and the solvent is dried and then supplied in the form of a film, 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. Alternatively, the ink may be supplied in a pattern by an inkjet method or a printing method. 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. Drying conditions can be appropriately selected according to the type of 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 50 to 90 ° C., depending on the type of 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 a laser beam 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 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 Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. 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 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 of 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, such as development time, developer aging, physical stimulation of the development shower, etc. 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 usually a spacer having a size of 2 to 8 μm is preferable. As described above, a photo spacer (PS) of a transparent resin film can be 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.

  Next, the present invention will be described more specifically with reference to synthesis, for example, Examples and Comparative Examples. However, the present invention is not limited to the following Examples unless it exceeds the gist. In the following, “part” represents “part by weight”.

[Synthesis of alkali-soluble unsaturated resin]
<Synthesis Example 1>
A flask equipped with a thermometer, a condenser, and a stirrer was purged with nitrogen gas, and then 100 parts of 5,5 ′-(1-methylethylidene) bis [2-cyclohexylphenol] (the following formula (1)) and epichlorohydrin 700 parts were charged and dissolved. Further, the mixture was heated to 65 ° C., 11 parts 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 (2). The obtained epoxy compound was white powder, and the epoxy equivalent was 257 g / eq.

  100 parts of the resulting epoxy compound, 29 parts of acrylic acid, 0.06 part of p-methoxyphenol, 2.6 parts of triphenylphosphine, and 126 parts of propylene glycol monomethyl ether acetate are charged into a reaction vessel, and further at 120 ° C. for 2 hours. 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 Example 2>
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.

<Synthesis Example 3>
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 were 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 Example 4>
Bisphenol A type epoxy compound (following formula (3), 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 polystyrene-equivalent weight average molecular weight of 2400 measured by GPC.

<Synthesis Example 5>
Bisphenol A type epoxy compound (formula (3), 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.

<Synthesis Example 6>
Fluorene bisphenol type epoxy compound (following formula (4), epoxy equivalent 231 g / eq) 100 parts, reaction mixture of succinic anhydride and tris (acryloyloxymethyl) ethanol (acid value 90.5) 273.2 parts, p- The reaction vessel was charged with 0.19 part of methoxyphenol, 7.4 parts of triphenylphosphine, and 368 parts of propylene glycol monomethyl ether acetate and stirred at 90 ° 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 1.0). Next, 6 parts of propylene glycol monomethyl ether acetate is added to 80 parts of the reaction solution obtained by the above reaction, 2.6 parts of isophorone diisocyanate is added and reacted at 90 ° C. for 3 hours, and trimellitic anhydride 4.1 is added. Part was added and reacted at 90 ° C. for 3 hours to obtain an alkali-soluble unsaturated resin (A-V) solution having an acid value of 57 and a polystyrene-equivalent weight average molecular weight of 2949 measured by GPC.

<Synthesis Example 7>
Fluorene bisphenol type epoxy compound (formula (4), epoxy equivalent 231 g / eq) 100 parts, reaction mixture of succinic anhydride and tris (acryloyloxymethyl) ethanol (acid number 90.5) 273.2 parts, p- The reaction vessel was charged with 0.19 part of methoxyphenol, 7.4 parts of triphenylphosphine, and 368 parts of propylene glycol monomethyl ether acetate and stirred at 90 ° 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 1.0). Next, 6 parts of propylene glycol monomethyl ether acetate is added to 80 parts of the reaction solution obtained by the above reaction, 1.9 parts of hexamethylene diisocyanate is added, and the mixture is reacted at 90 ° C. for 3 hours, and trimellitic anhydride 3. 8 parts were added and reacted at 90 ° C. for 3 hours to obtain an alkali-soluble unsaturated resin (A-VI) solution having an acid value of 52 and a polystyrene-equivalent weight average molecular weight of 3113 measured by GPC.

<Synthesis Example 8>
“XD-1000” manufactured by Nippon Kayaku Co., Ltd. (polyglycidyl ether of dicyclopentadiene / phenol polymer, weight average molecular weight 700, epoxy equivalent 252 g / eq) 75.1 parts, bisphenol type epoxy compound synthesized in Synthesis Example 1 ( 76 parts of the formula (2)), 43.8 parts of acrylic acid, 0.06 part of p-methoxyphenol, 2.4 parts of triphenylphosphine, and 136.8 parts of propylene glycol monomethyl ether acetate were charged in a reaction vessel, The mixture was stirred at 0 ° C. until the acid value was 3.0 mg-KOH / g or less. It took 12 hours for the acid value to reach the target (acid value 2). Next, 197 parts of propylene glycol monomethyl ether acetate was added to the reaction solution obtained by the above reaction, 22.6 parts of isophorone diisocyanate and 0.02 part of dibutyltin dilaurate were added, and the mixture was reacted at 90 ° C. for 3 hours. Further, 29.4 parts of tetrahydrophthalic anhydride and 33.7 parts of trimellitic anhydride were added, reacted at 90 ° C. for 4 hours, acid value of 100, and an alkali-soluble solvent having a polystyrene equivalent weight average molecular weight of 4000 measured by GPC. A saturated resin (A-VII) solution was obtained.

<Synthesis Example 9>
77.7 parts of bisphenol (formula (1)) used in Synthesis Example 1, 56.6 parts of glycidyl methacrylate, 0.06 part of p-methoxyphenol, 2.6 parts of triphenylphosphine, and 126 of propylene glycol monomethyl ether acetate The reaction mixture was charged into a reaction vessel and reacted at 100 ° C. for 15 hours to obtain a reaction solution.
60 parts of propylene glycol monomethyl ether acetate is added to 263 parts of the reaction solution, 10.7 parts of hexamethylene diisocyanate is added, the mixture is reacted at 90 ° C. for 3 hours, and 28.5 parts of trimellitic anhydride is further added. The mixture was further reacted at 3 ° C. for 3 hours to obtain an alkali-soluble unsaturated resin (A-VIII) solution having an acid value of 95 and a weight-average molecular weight of 2300 in terms of polystyrene measured by GPC.

[Black matrix formation evaluation]
<Example 1>
60 parts by weight (30 parts by weight in terms of solid content) of the alkali-soluble unsaturated resin (AI) solution obtained in Synthesis Example 1, 10 parts by weight of dipentaerythritol hexaacrylate, “CGI-242” (Ciba Specialty) Carbon black dispersion made by Te Chemical Co., Ltd. (Structural formula is as follows) 4 parts by weight, dispersion using Big Chemie Japan Co., Ltd. trade name “Disperbyk182” as urethane-based nitrogen atom-containing polymer dispersant A photosensitive black resin composition was obtained by mixing 224 parts of a body solution (56 parts by weight in terms of solid content, of which 43 parts by weight of carbon black and 13 parts by weight of a polymer dispersant) was mixed with 218 parts by weight of propylene glycol monomethyl ether acetate. .

  The photosensitive black resin composition thus obtained was spin-coated on a 10 cm square glass substrate and dried on a hot plate at 90 ° C. for 150 seconds. The film thickness after drying was 1 μm. Next, this sample was image-exposed with a high-pressure mercury lamp through a mask, and then subjected to spray development using a KOH aqueous solution at a temperature of 23 ° C. and a concentration of 0.1% by weight to form a black pixel (black matrix).

<Example 2>
A photosensitive black resin composition was obtained in the same manner as in Example 1 except that the alkali-soluble unsaturated resin (AI) was changed to the alkali-soluble unsaturated resin (A-III), and a black pixel was formed.

<Example 3>
A photosensitive black resin composition was obtained in the same manner as in Example 1 except that the alkali-soluble unsaturated resin (AI) was changed to the alkali-soluble unsaturated resin (A-VII), and further black pixels were formed.

<Example 4>
A photosensitive black resin composition was obtained in the same manner as in Example 1 except that the alkali-soluble unsaturated resin (AI) was changed to the alkali-soluble unsaturated resin (A-VIII), and further black pixels were formed.

<Comparative Example 1>
A photosensitive black resin composition was obtained in the same manner as in Example 1 except that the alkali-soluble unsaturated resin (AI) was changed to the alkali-soluble unsaturated resin (A-II), and a black pixel was formed.

  The photosensitive black resin composition prepared in Examples 1 to 4 and Comparative Example 1 and the formed pixels were evaluated on the following items, and the results are shown in Table 1.

<Adhesion>
The minimum pattern size of a resist that can be resolved at an exposure amount that faithfully reproduces a 20 μm mask pattern was observed with a microscope at a magnification of 200 times. The minimum pattern dimension was 10 μm or less, and the adhesion ○, and the one exceeding 10 μm was defined as the adhesion X.

<Pixel sharpness>
The shape of the fine black pixel at an exposure amount that faithfully reproduces a 20 μm mask pattern was observed with a microscope at a magnification of 1000 times. Those having good linearity were designated as pixel sharpness ○, and resist patterns having protrusions and irregularities were designated as pixel sharpness x.

<Storage stability>
The photosensitive black resin composition was stored for two weeks under two conditions of 35 ° C. and 10 ° C., and the time required for developing the film in the unexposed area was compared. When the development time changed by 10% or more, the storage stability x, when the change rate was less than 5%, the storage stability ○, and less than 1%, the storage stability ◎.

  From Table 1, according to the present invention using a specific alkali-soluble unsaturated resin, a pixel having a good edge shape can be formed by a photosensitive colored resin composition having excellent storage stability and adhesion to a substrate. I understand that I can do it.

[Photo spacer formation evaluation]
<Examples 5 to 9 and Comparative Example 2>
(1) Preparation of photosensitive resin composition 100 parts (solid content) of an alkali-soluble unsaturated resin shown in Table 2 and dipentaerythritol hexaacrylate (“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable monomer 80 Part, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone (“Irgacure 907” manufactured by Ciba-Gaigi Co., Ltd.) as a photopolymerization initiator, and a fluorosurfactant ( Dainippon Ink & Chemicals Co., Ltd. “Megafac F475”) 0.01 part and 3-glycidoxypropyltrimethoxysilane (Toray Dow Corning “SH6040”) 5 parts as a silane coupling material were mixed, Dissolve in propylene glycol monomethyl ether acetate so that the solid content concentration is 35% by weight. After, and filtered through a Millipore filter (0.2 [mu] m), to obtain a photosensitive resin composition.

(2) Formation of spacer pattern After applying the above resin composition on the ITO film of the glass substrate having an ITO film formed on the surface using a spinner, the coating was heated and dried on a hot plate at 80 ° C. for 3 minutes. A film was formed. The obtained coating film was exposed to an exposure amount of 100 mJ / cm ² using ultraviolet rays having an intensity at 365 nm of 32 mW / cm ² using a predetermined pattern mask. The ultraviolet irradiation at this time was performed under air. Next, spray development was carried out with a 0.1% KOH aqueous solution at 23 ° C. for twice the minimum development time, and then rinsed with pure water for 1 minute. Here, the minimum development time means a time during which the unexposed area is completely dissolved under the same development conditions. By these operations, unnecessary portions were removed and a spacer pattern of 10 μm × 10 μm could be obtained. The substrate on which the spacer pattern was formed was cured by heating in an oven at 235 ° C. for 30 minutes to obtain a spacer pattern having a height of 4 μm.

(3) Evaluation of recovery rate and elasticity The recovery rate by load loading / unloading of the spacer pattern obtained in (2) above was determined by a load-unloading test using Shimadzu Dynamic Ultra Hardness Tester “DUH-W201S”. evaluated. A load was applied to the spacer at a constant speed (0.22 gf / sec) with a flat indenter with a diameter of 50 μm at a measurement temperature of 23 ° C. and held for 5 seconds when the load reached 5 gf, and then unloaded at the same speed. Went. From this test, the maximum displacement H [max] and the final displacement H [Last] shown in FIG. 1 are obtained, and the recovery rate (%) = (H [max] −H [last]) / H [max] × 100 is calculated. The results are shown in Table 2.

  Further, as an index of elasticity, a load N (gf) when the displacement under load was 0.25 μm was obtained, and the result is shown in Table 2.

(4) Evaluation of load N (gf) when displacement under load is 0.25 μm Change in viscosity between the obtained photosensitive resin composition kept sealed at 70 ° C. for 72 hours and left at room temperature The degree of was calculated from the following formula.
Degree of change (%) = ((viscosity of products stored at 70 ° C. for 72 hours) − (viscosity of products stored at room temperature)))
/ (Viscosity of room temperature storage product) x 100

  Storage stability where the absolute value of the degree of change was less than 3% ◎ Storage stability when less than 5% ○ Storage stability x when 5% or more. The greater the degree of change, the lower the stability of the stored product.

  From Table 2, it can be seen that according to the present invention using a specific alkali-soluble unsaturated resin, a photosensitive resin composition excellent in storage stability can form a spacer excellent in handleability after long-term storage. .

It is a schematic diagram which shows the maximum displacement H [max] and the last displacement H [Last] of the load-unloading test in photospacer formation evaluation.

Claims (7)

A photosensitive resin composition containing an organic binder, wherein the organic binder comprises an epoxy compound (a) having at least two epoxy groups in the molecule, an unsaturated group-containing carboxylic acid (b), An alkali-soluble unsaturated resin obtained by further reacting the reaction product with a compound (c) having an isocyanate group ,
The epoxy compound (a) having at least two epoxy groups in the molecule includes a compound represented by the following general formula (Ia), and the following general formula (II) is represented by the following general formula (IIAa) or ( A photosensitive resin composition represented by IIAb) .

(In the general formulas (IIAa) and (IIAb), R ¹ and R ² have the same meaning as in the general formula (II).) A photosensitive resin composition containing an organic binder, wherein the organic binder comprises a phenolic hydroxyl group-containing compound (f) having at least two or more phenolic hydroxyl groups in the molecule, and an unsaturated group-containing epoxy compound. A phenolic compound containing an alkali-soluble unsaturated resin obtained by further reacting the reaction product with (g) with a compound (c) having an isocyanate group, and having at least two phenolic hydroxyl groups in the molecule; The photosensitive compound, wherein the hydroxyl group-containing compound (f) includes a compound represented by the following general formula (If), and the following general formula (II) is represented by the following general formula (IIAa) or (IIAb): Resin composition.

(In the general formulas (IIAa) and (IIAb), R ¹ and R ² have the same meaning as in the general formula (II).) 3. The photosensitive resin composition according to claim 1, wherein the compound (c) having an isocyanate group is a compound having two or more isocyanate groups in the molecule. The photosensitive resin composition according to any one of claims 1 to 3 , further comprising a photopolymerization initiator. In any one of claims 1 to 4, the photosensitive resin composition further contains a colorant. The color filter formed using the photosensitive resin composition of any one of Claims 1 thru | or 5 . The liquid crystal display device which has a member formed using the photosensitive resin composition of any one of Claim 1 thru | or 5 .

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