JP5495991B2 - Colored photosensitive resin composition, cured film and method for producing the same, color filter, and display device - Google Patents

Description

  The present invention relates to a colored photosensitive resin composition, a cured film and a method for producing the same, a color filter, and a display device.

The color filter is an indispensable component for various display devices such as a liquid crystal display and an organic EL display.
In recent years, especially for color filters for TV applications, higher image quality, that is, improvement in contrast and color purity, is required compared to conventional monitor applications. In addition, studies on improving the brightness of color filters have been actively conducted mainly for the purpose of reducing power consumption.
Further, in order to improve the reliability of the colored photosensitive resin composition, it is considered effective to strengthen the crosslinking of the cured film. For example, in order to improve chemical resistance, in the colored photosensitive resin composition An attempt has been made to add a resin containing an oxetanyl group and a carboxyl group or a phenolic hydroxyl group (see Patent Document 1).

JP 2007-292840 A

An object of the present invention is to provide a colored photosensitive resin composition having a large development margin and excellent heat resistance, light resistance and solvent resistance, a cured film obtained by curing the colored photosensitive resin composition, and the cured film. It is an object to provide a color filter provided and a liquid crystal display device provided with the color filter.
In the present invention, the “development margin” refers to a margin with respect to the development time of a change in developed line width at the time of development.

The above-mentioned problems of the present invention have been solved by means described in the following <1>, <9>, <10>, <11> or <13>. It is described below together with <2> to <8> and <12> which are preferred embodiments.
<1> (Component A) a structural unit (a1) having a residue in which a carboxyl group and / or a phenolic hydroxyl group is protected with a thermally decomposable group, a structural unit (a2) having an epoxy group and / or an oxetanyl group, and , A copolymer containing at least a structural unit (a3) having a carboxyl group and / or a phenolic hydroxyl group, (Component B) a radiation-sensitive radical polymerization initiator, (Component C) an ethylenically unsaturated compound, and (Component D) a colored photosensitive resin composition comprising a colorant,
<2> The colored photosensitive resin composition according to <1>, wherein the structural unit (a1) is a structural unit represented by the formula (A2).

（式（Ａ２）中、Ｒ¹及びＲ²は、それぞれ独立に水素原子、アルキル基又はアリール基を表し、少なくともＲ¹及びＲ²のいずれか一方が前記アルキル基又はアリール基であり、Ｒ³は、アルキル基又はアリール基を表し、Ｒ¹又はＲ²とＲ³とが連結して環状エーテルを形成してもよく、Ｒ⁴は、水素原子又はメチル基を表し、Ｘは単結合又はアリーレン基を表す。）

(In Formula (A2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least ^one of R ¹ and R ² is the alkyl group or aryl group, and R ³ Represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene Represents a group.)

<3> The colored photosensitive resin composition according to the above <1> or <2>, wherein the structural unit (a2) has an oxetanyl group,
<4> The colored photosensitive resin composition according to any one of the above <1> to <3>, wherein Component B includes at least an oxime ester compound,
<5> The colored photosensitive resin composition according to any one of <1> to <4>, wherein the component B includes at least a hexaarylbiimidazole compound,
<6> The colored photosensitive resin composition according to any one of the above <1> to <5>, wherein the component D includes at least a pigment having an average primary particle diameter in the range of 10 to 30 nm.
<7> The colored photosensitive resin composition according to any one of the above <1> to <6>, wherein the component D includes at least a dye,
<8> The colored photosensitive resin composition according to any one of the above <1> to <7>, which is for laser exposure in a wavelength range of 300 to 420 nm,
<9> A cured film produced from the colored photosensitive resin composition according to any one of <1> to <8> above,
<10> A film forming step of forming a film on a substrate with the colored photosensitive resin composition according to any one of the above <1> to <8>, an exposure step of exposing the film with actinic rays, and exposure A development process for developing the film with an aqueous developer, and a post-baking process for thermosetting the developed film,
<11> A color filter comprising the cured film according to <9> or the cured film obtained by the production method according to <10>,
<12> The color filter according to <11>, wherein the cured film is provided on an array.
<13> A display device comprising the color filter according to <11> or <12>.

  According to the present invention, a colored photosensitive resin composition having a large development margin and excellent in heat resistance, light resistance and solvent resistance, a cured film obtained by curing the colored photosensitive resin composition, and the cured film It was possible to provide a color filter provided, and a liquid crystal display device provided with the color filter.

  Hereinafter, the present invention will be described in detail. In addition, in this invention, description of "A-B" showing a numerical range means "A or more and B or less" unless there is particular notice, and means the numerical range containing A and B which are endpoints.

I. Colored photosensitive resin composition The colored photosensitive resin composition of the present invention comprises (Component A) a structural unit (a1) having a residue in which a carboxyl group and / or a phenolic hydroxyl group is protected with a thermally decomposable group, an epoxy group. And / or a copolymer containing at least the structural unit (a2) having an oxetanyl group and the structural unit (a3) having a carboxyl group and / or a phenolic hydroxyl group, (Component B) a radiation-sensitive radical polymerization initiator, It comprises (Component C) an ethylenically unsaturated compound and (Component D) a colorant.
The colored photosensitive resin composition of the present invention can be suitably used as a colored photosensitive resin composition for color filters.
In addition, the colored photosensitive resin composition of the present invention comprises, as necessary, (component E) solvent, (component F) adhesion improver, (component G) polymerization inhibitor, (component H) surfactant, (component) I) You may contain a crosslinking agent etc.
Hereinafter, each component will be described.

(Component A) The copolymer The colored photosensitive resin composition of the present invention comprises (Component A) a structural unit (a1) having a residue in which a carboxyl group and / or a phenolic hydroxyl group is protected with a thermally decomposable group, A copolymer containing at least a structural unit (a2) having an epoxy group and / or an oxetanyl group and a structural unit (a3) having a carboxyl group and / or a phenolic hydroxyl group is contained.
Component A is preferably alkali-soluble.

Component A is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. “(Meth) acrylic acid” is synonymous with “acrylic acid and / or methacrylic acid”. In addition, you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene or a vinyl compound.
Component A preferably contains a structural unit derived from (meth) acrylic acid and / or an ester thereof in an amount of 50 mol% or more, more preferably 90 mol% or more, more preferably 100 mol, based on all the structural units. % Content is particularly preferable.

The method for introducing the structural unit contained in component A may be a polymerization method, a polymer reaction method, or a combination of these two methods.
In the polymerization method, for example, an ethylenically unsaturated compound having a residue in which an acid group is protected by a thermally decomposable group, an ethylenically unsaturated compound having an epoxy group or an oxetanyl group, a carboxyl group and / or a phenolic hydroxyl group A target copolymer can be obtained by addition polymerization of an ethylenically unsaturated compound containing
In the polymer reaction method, an epoxy group can be introduced by reacting a copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate with epichlorohydrin. In this way, after copolymerizing an ethylenically unsaturated compound having a reactive group, the reactive group remaining in the side chain is utilized to protect the phenolic hydroxyl group or carboxyl group with a thermally decomposable group by a polymer reaction. Functional groups such as epoxy groups or oxetanyl groups can be introduced into the side chain.

<Structural unit (a1)>
Component A is a structural unit (a1) having a residue in which a carboxyl group and / or a phenolic hydroxyl group is protected with a thermally decomposable group (also simply referred to as “structural unit (a1)”. The same applies to other structural units. Contain). When component A has the structural unit (a1), it is possible to achieve both development margins and mechanical properties.

(A1-1) Structural unit having a residue in which a carboxyl group is protected with a thermally decomposable group Structural unit having a residue in which a carboxyl group (hereinafter also referred to as “carboxy group”) is protected with a thermally decomposable group As (a1-1), the structural unit which has the residue in which the carboxy group contained in the structural unit as described in the following (a1-1-1) and (a1-1-2) is protected with a thermally decomposable group. It is preferable that

(A1-1-1) Structural unit having a carboxy group As the structural unit (a1-1-1) having a carboxy group, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated tricarboxylic acid, or the like is included in the molecule. Examples thereof include a structural unit derived from an unsaturated carboxylic acid having at least one carboxy group.
Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polyvalent carboxylic acid may be its acid anhydride, and specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (2- (meth) acryloyloxyalkyl) ester of a polyvalent carboxylic acid, for example, succinic acid mono (2- (meth) acryloyloxyethyl). And mono (2- (meth) acryloyloxyethyl) phthalate. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone mono (meth) acrylate. As the unsaturated carboxylic acid, (meth) acrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used. Among them, from the viewpoint of developability, in order to form a structural unit having a carboxy group, it is preferable to use (meth) acrylic acid or an anhydride of an unsaturated polyvalent carboxylic acid, and (meth) acrylic acid is used. It is more preferable.
The structural unit (a1-1-1) having a carboxy group may be composed of one kind alone, or may be composed of two or more kinds.

(A1-1-2) Structural unit having both an ethylenically unsaturated group and an acid anhydride residue The structural unit (a1-1-2) having both an ethylenically unsaturated group and an acid anhydride residue is A unit derived from a monomer obtained by reacting a hydroxyl group present in a structural unit having an ethylenically unsaturated group with an acid anhydride is preferable.
As the acid anhydride, known ones can be used, and specific examples include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride and the like. Examples include basic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and biphenyl tetracarboxylic acid anhydride. Among these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, from the viewpoint of developability.

(A1-1) A structural unit having a residue in which a carboxy group is protected with a thermally decomposable group A structural unit having a residue in which a carboxy group is protected with a thermally decomposable group is the structural unit (a1-1-1- 1) A structural unit having a residue in which a carboxy group contained in the structural unit (a1-1-2) is protected by a thermally decomposable group.

Furthermore, among the thermally decomposable groups, it is more preferable from the viewpoint of sensitivity that the carboxy group is a residue protected with an acetal or ketal represented by the formula (A1). In addition, when the carboxy group is an acetal or ketal-protected residue represented by the formula (A1), the residue as a whole is — (C═O) —O—CR ¹ R ² (OR ³ ). It has a structure.

（式（Ａ１）中、Ｒ¹及びＲ²はそれぞれ独立に、水素原子、アルキル基、又は、アリール基を表し、少なくともＲ¹及びＲ²のいずれか一方が前記アルキル基、又は、アリール基であり、Ｒ³は、アルキル基、又は、アリール基を表し、Ｒ¹又はＲ²とＲ³とが連結して環状エーテルを形成してもよい。）

(In Formula (A1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least ^one of R ¹ and R ² is the alkyl group or aryl group. R ³ represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether.)

The alkyl group for R ¹ , R ² and R ³ may be linear, branched or cyclic.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group. Of these, a methyl group and an ethyl group are preferable.
The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms.
Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group. Among these, monocyclic ones are preferable and cyclohexyl groups are preferable.
The alkyl group may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, aryl group having 6 to 20 carbon atoms, and 1 to 6 carbon atoms. The alkoxy group of can be illustrated. When it has a halogen atom as a substituent, R ¹ , R ² and R ³ become a haloalkyl group, and when it has an aryl group as a substituent, R ¹ , R ² and R ³ become an aralkyl group. As the aralkyl group, a benzyl group is preferable.

The aryl group in R ^1, R ² and R ^3, preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a silyl group, a cumenyl group, and a 1-naphthyl group, and a phenyl group is preferable.

R ¹ , R ² and R ³ can be bonded together to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ¹ and R ² , R ¹ and R ³ or R ² and R ³ are bonded include, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydro group. A pyranyl group etc. can be mentioned.

In formula (A1), it is preferable that either R ¹ or R ² is a hydrogen atom or a methyl group.
As the radically polymerizable monomer used for forming the structural unit having the residue represented by the formula (A1), a commercially available one may be used, for example, paragraph of JP2009-098616A You may use what was synthesize | combined by well-known methods, such as the method of 0025-0026.

  As the structural unit (a1-1) having a residue in which a carboxy group is protected with a thermally decomposable group, a structural unit represented by the formula (A2) is more preferable.

（式（Ａ２）中、Ｒ¹及びＲ²は、それぞれ独立に水素原子、アルキル基又はアリール基を表し、少なくともＲ¹及びＲ²のいずれか一方が前記アルキル基又はアリール基であり、Ｒ³は、アルキル基又はアリール基を表し、Ｒ¹又はＲ²とＲ³とが連結して環状エーテルを形成してもよく、Ｒ⁴は、水素原子又はメチル基を表し、Ｘは単結合又はアリーレン基を表す。）

(In Formula (A2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least ^one of R ¹ and R ² is the alkyl group or aryl group, and R ³ Represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene Represents a group.)

Wherein (A2), R ¹ ~R ³ is the same meaning as R ¹ to R ³ in the formula (A1), and preferred ranges are also the same.
In Formula (A2), R ¹ and R ² are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R ³ is preferably a linear, branched or cyclic alkyl group having 6 or less carbon atoms or an aralkyl group having 7 to 10 carbon atoms, more preferably an ethyl group, a cyclohexyl group or a benzyl group. The cyclic ether in which R ¹ or R ² and R ³ are linked is preferably a tetrahydropyranyl group or a tetrahydrofuranyl group. R ⁴ is preferably a methyl group. X is preferably a single bond or a phenylene group.

  Preferable specific examples of the structural unit (a1-1) include the following structural units. R represents a hydrogen atom or a methyl group.

(A1-2) Structural unit having a residue in which a phenolic hydroxyl group is protected with a thermally decomposable group The structural unit (a1-2) having a residue in which a phenolic hydroxyl group is protected with a thermally decomposable group is described below. The structural unit having a residue obtained by protecting the structural unit having a phenolic hydroxyl group described in (a1-2-1) with a thermally decomposable group is preferable.

(A1-2-1) Structural unit having a phenolic hydroxyl group Examples of the structural unit (a1-2-1) having a phenolic hydroxyl group include a hydroxystyrene structural unit and a structural unit in a novolac resin. Among them, a structural unit derived from α-methylhydroxystyrene is preferable from the viewpoint of transparency. Among the structural units having a phenolic hydroxyl group, the structural unit represented by the formula (A4) is preferable from the viewpoints of transparency and sensitivity.

（式（Ａ４）中、Ｒ²⁰は水素原子又はメチル基を表し、Ｒ²¹は単結合又は二価の連結基を表し、Ｒ²²はそれぞれ独立にハロゲン原子又はアルキル基を表し、ａは１〜５の整数を表し、ｂは０〜４の整数を表し、ａ＋ｂは５以下である。）

(In the formula (A4), R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ represents a single bond or a divalent linking group, R ²² each independently represents a halogen atom or an alkyl group, 5 represents an integer of 5, b represents an integer of 0 to 4, and a + b is 5 or less.)

R ²⁰ is preferably a methyl group.
R ²¹ is preferably a single bond or an ester bond. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.

Moreover, although a represents the integer of 1-5, from the viewpoint of the effect of this invention, and the point that manufacture is easy, it is preferable that a is 1 or 2, and it is more preferable that a is 1. .
Further, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R ²¹ is the reference (first position).
R ²² is a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, or a linear or branched alkyl group having 1 to 5 carbon atoms. Among these, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable because of easy production.

(A1-2) Structural unit having a residue in which a phenolic hydroxyl group is protected with a thermally decomposable group A structural unit (a1-2) having a residue in which a phenolic hydroxyl group is protected with a thermally decomposable group is phenolic. This is a structural unit having a residue in which the phenolic hydroxyl group of the structural unit (a1-2-1) having a hydroxyl group is protected by a thermally decomposable group.
The phenolic hydroxyl group is more preferably a residue protected with an acetal or ketal represented by the formula (A1) from the viewpoint of sensitivity. In this case, the residue as a whole has a structure of —Ar—O—CR ¹ R ² (OR ³ ). Ar represents an arylene group.
Preferable examples of the acetal ester structure of the phenolic hydroxyl group include a combination of R ¹ = R ² = R ³ = methyl group, R ¹ = R ² = methyl group and R ³ = benzyl group.

  Examples of the radical polymerizable monomer used to form a structural unit having a residue in which a phenolic hydroxyl group is protected with a thermally decomposable group include, for example, 1-alkoxyalkyl protected form of hydroxystyrene, hydroxystyrene Tetrahydropyranyl protector of hydroxystyrene, tetrahydrofuranyl protector of hydroxystyrene, 1-alkoxyalkyl protector of α-methylhydroxystyrene, tetrahydropyranyl protector of α-methylhydroxystyrene, and tetrahydrofuranyl protector of α-methylhydroxystyrene 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate, tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate, and the like. Of these, a 1-alkoxyalkyl protector of α-methylhydroxystyrene is preferred.

  Specific examples of the thermal decomposable group protection of the phenolic hydroxyl group include a 1-alkoxyalkyl group and a tetrahydrofuranyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexyl) An ethoxy) ethyl group, a 1-benzyloxyethyl group, etc. can be mentioned, Among these, a 1-ethoxyethyl group is preferable. These can be used alone or in combination of two or more.

  A commercially available thing may be used for the radically polymerizable monomer used in order to form a structural unit (a1-2), and what was synthesize | combined by the well-known method can also be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.

  Preferable specific examples of the structural unit (a1-2) include the following structural units, but the present invention is not limited thereto. R represents a hydrogen atom or a methyl group.

  In the structural unit constituting Component A, the content of the structural unit (a1) is preferably 5 to 50 mol% in the copolymer of Component A, from the viewpoints of heat resistance, reliability and developability. -40 mol% is more preferable. The “structural unit constituting component A” in the present invention means a structural unit derived from one monomer constituting component A, that is, a monomer unit or one monomer unit constituting component A is modified. Refers to the structural unit obtained. The content of each structural unit in Component A corresponds to the copolymerization ratio of each monomer copolymerized to synthesize Component A.

<Structural unit (a2)>
Component A contains the structural unit (a2) having an epoxy group and / or an oxetanyl group.
The epoxy group and the oxetanyl group react with a carboxy group or a phenolic hydroxyl group by heat treatment to form a covalent bond to cause a crosslinking reaction.
The structural unit (a2) having an epoxy group and / or oxetanyl group is preferably a structural unit having an alicyclic epoxy group and / or oxetanyl group, and more preferably a structural unit having an oxetanyl group.
The structural unit having an epoxy group and / or oxetanyl group only needs to have at least one epoxy group or oxetanyl group in one structural unit, and has a total of 1 to 3 epoxy groups and / or oxetanyl groups. It is more preferable to have one or two epoxy groups and / or oxetanyl groups in total, and it is even more preferable to have one epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, α-ethyl ( Glycidyl acrylate, glycidyl α-n-propyl (meth) acrylate, glycidyl α-n-butyl (meth) acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-6 , 7-epoxyheptyl, α-ethyl (meth) acrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, paragraph of Japanese Patent No. 4168443 Compounds containing an alicyclic epoxy skeleton according to any one of 0031 to 0035 Etc., and the like.
Specific examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include, for example, a (meth) acryl having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Examples include acid esters.
In the present invention, the radical polymerizable monomer used for forming the structural unit (a2) is preferably a monomer containing a (meth) acrylate structure.

  Among these monomers, more preferred are compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and paragraphs 0011 to 0016 of JP 2001-330953 A. (Meth) acrylic acid esters having an oxetanyl group, particularly preferred are (meth) acrylic acid esters having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Among these, preferred are (meth) acrylic acid 3,4-epoxycyclohexylmethyl and (meth) acrylic acid (3-ethyloxetan-3-yl) methyl, and most preferred is (meth) acrylic acid (3 -Ethyloxetane-3-yl) methyl. These structural units can be used alone or in combination of two or more.

  The structural unit (a2) is a residue obtained by removing one hydrogen atom from the structures represented by the formulas (A5-1) to (A5-3), or the formula (A6-1) or the formula (A6-2) It is preferable to have a residue represented by:

（式（Ａ６−１）及び式（Ａ６−２）中、Ｒ^1b及びＲ^6bはそれぞれ独立に、水素原子又はアルキル基を表し、Ｒ^2b、Ｒ^3b、Ｒ^4b、Ｒ^5b、Ｒ^7b、Ｒ^8b、Ｒ^9b及びＲ^10bはそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、又は、アリール基を表す。）

(In Formula (A6-1) and Formula (A6-2), R ^1b and R ^6b each independently represent a hydrogen atom or an alkyl group, and R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b each independently represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group.

In formula (A6-1) and formula (A6-2), R ^1b and R ^6b each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, More preferably, it is an atom or an alkyl group having 1 to 5 carbon atoms.
R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group.
As a halogen atom, a fluorine atom and a chlorine atom are more preferable, and a fluorine atom is still more preferable.
The alkyl group may be linear, branched or cyclic. The linear and branched alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. The cyclic alkyl group preferably has 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 5 to 7 carbon atoms. The linear and branched alkyl groups may be substituted with a cyclic alkyl group, and the cyclic alkyl group may be substituted with a linear and / or branched alkyl group.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms.
The alkyl group and aryl group may further have a substituent.
Among these, R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, Or it is more preferable that it is a C1-C4 perfluoroalkyl group.

  Preferable specific examples of the structural unit (a2) include the following structural units. R represents a hydrogen atom or a methyl group.

  In the present invention, it is preferable that the structural unit (a2) has an oxetanyl group from the viewpoint of luminance.

  In the structural unit constituting Component A, the content of the structural unit (a2) is preferably 10 to 60 mol%, more preferably 20 to 50 mol%, from the viewpoints of luminance, heat resistance, and reliability.

<Structural unit (a3)>
Component A contains a structural unit (a3) having a carboxy group and / or a phenolic hydroxyl group. In the present invention, the carboxy group includes a carboxylic anhydride residue.
As the radical polymerizable monomer used for forming the structural unit having a carboxy group, those described in the description of the structural unit having a carboxy group (a1-1-1) can be preferably used.
As the structural unit having a phenolic hydroxyl group, those described in the description of (a1-2-1) the structural unit having a phenolic hydroxyl group can be preferably used.
Among these, as the structural unit (a3), the unsaturated group selected from the group consisting of (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, α-methylhydroxystyrene, and hydroxystyrene. Preferred examples include structural units derived from carboxylic acids.
These structural units can be used individually by 1 type or in combination of 2 or more types.

  Preferable specific examples of the structural unit (a3) include the following structural units. R represents a hydrogen atom or a methyl group.

  The content of the structural unit (a3) is preferably 10 to 60 mol%, more preferably 20 to 50 mol%, from the viewpoint of achieving both developability and reliability.

<Other structural units>
Component A may contain other structural units other than the structural units (a1) to (a3) as long as the effects of the present invention are not hindered. Examples of the radical polymerizable monomer used to form other structural units include the compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 (provided that the structural units ( excluding compounds forming a1) to (a3)).
Among these, from the viewpoint of luminance, heat resistance and reliability, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid dicyclopentenyl, (meth) acrylic acid cyclohexyl-containing (meth) ) Acrylic esters are preferred. From the viewpoint of luminance, methyl (meth) acrylate is preferred. From the viewpoint of developability, 2-hydroxyethyl (meth) acrylate and alkyl-terminated polyalkylene glycol (meth) acrylate are preferred. Among these, 2-hydroxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and methyl (meth) acrylate are more preferable. Other structural units can be used alone or in combination of two or more.
In all the structural units constituting Component A, the content of other structural units is preferably from 0 to 30 mol%, more preferably from 5 to 25 mol%.

  The weight average molecular weight of Component A is preferably 3,000 to 100,000, and more preferably 5,000 to 50,000. In addition, the weight average molecular weight in this invention is a polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC) when tetrahydrofuran (THF) is used as a solvent.

  Various methods for synthesizing the copolymer of the component A are known. For example, at least the structural unit (a1), the structural unit (a2), and the structural unit (a3) are formed. And a method of synthesizing a mixture of radically polymerizable monomers containing a radically polymerizable monomer used for the purpose of polymerization in an organic solvent using a radical polymerization initiator.

Hereinafter, although preferable thing is illustrated as a component A used by this invention, this invention is not limited to this.
1-ethoxyethyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / glycidyl methacrylate / methacrylic acid copolymer 1-ethoxyethyl methacrylate / 2-hydroxyethyl methacrylate / 3,4-epoxycyclohexyl methacrylate Methyl / methacrylic acid copolymer 1-ethoxyethyl methacrylate / 2-hydroxyethyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester / methacrylic acid Acid copolymer 1-ethoxyethyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid copolymer 1- (Cyclohexyloxy) ethyl phosphate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / 2-hydroxyethyl methacrylate copolymer 1-ethoxyethyl methacrylate / methacrylic acid / hydroxystyrene / methacrylic acid Acid (3-ethyloxetane-3-yl) methyl / 2-hydroxyethyl methacrylate copolymer 1-ethoxyethyl acrylate / acrylic acid / acrylic acid (3-ethyloxetane-3-yl) methyl / acrylic acid 2- Hydroxyethyl copolymer 1-ethoxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / styrene copolymer 1-ethoxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / Dicyclopentanyl methacrylate copolymer Tetrahydrofuran-2-yl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer Tetrahydrofuran-2-yl methacrylate / methacrylic acid / methacrylic acid (3-ethyl Oxetane-3-yl) methyl / 2-hydroxyethyl methacrylate copolymer Component A can be used alone or in combination of two or more.

The content of Component A in the colored photosensitive resin composition of the present invention is preferably 1 to 50% by weight, and preferably 5 to 40% by weight, based on the total solid content of the colored photosensitive resin composition. It is more preferable that the content is 5 to 35% by weight. When the content is within this range, the development margin, heat resistance and reliability are improved. The solid content of the colored photosensitive resin composition represents an amount excluding volatile components such as a solvent.
In addition, in the colored photosensitive resin composition of this invention, you may use together resin other than the component A in the range which does not prevent the effect of this invention. However, the content of the resin other than component A is preferably smaller than the content of component A from the viewpoint of heat resistance and reliability.

  As the resin other than Component A, a polymer having a carboxylic acid in the side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxylic acid, polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.

  Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable. In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. The polymer can be used by mixing in an arbitrary amount.

In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. Is mentioned.
Examples of other alkali-soluble binder resins include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, and JP-A-11-174224. JP-A 2000-56118, JP-A 2003-233179, JP-A 2009-52020, and the like can be used.

(Component B) Radiation-sensitive radical polymerization initiator As the radiation-sensitive radical polymerization initiator (hereinafter, also simply referred to as “photopolymerization initiator”), it is sensitized by exposure light, and the (Component C) ethylenic unsaturated compound is used. A compound that initiates and accelerates the polymerization of a compound. A compound that is sensitive to actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and that initiates and accelerates the polymerization of the (component C) ethylenically unsaturated compound is preferable. In addition, a radiation-sensitive radical polymerization initiator that is not directly sensitive to actinic rays having a wavelength of 300 nm or more can be combined with a sensitizer as long as it is a compound that is sensitive to actinic rays having a wavelength of 300 nm or more when used in combination with a sensitizer. It can be preferably used.

Examples of the photopolymerization initiator include oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxides, azo compounds, coumarin compounds, azide compounds, metallocenes. Examples include compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, and acylphosphine (oxide) compounds.
Among these, oxime ester compounds and hexaarylbiimidazole compounds are preferable from the viewpoint of sensitivity.

  Examples of the oxime ester compound include JP 2000-80068 A, JP 2001-233842 A, JP 2004-534797 A, International Publication No. 2005/080337, International Publication No. 2006/018933, and JP 2007-2007 A. The compounds described in Japanese Patent No. 210991, Japanese Patent Application Laid-Open No. 2007-231000, Japanese Patent Application Laid-Open No. 2007-267979, Japanese Patent Application Laid-Open No. 2009-191061, and International Publication No. 2009/131189 can be used.

  The oxime ester compound is preferably a compound represented by the following formula (1) or a compound represented by the following formula (2). The oxime ester compound may be either E-form or Z-form, or a mixture of E-form and Z-form.

（式（１）及び式（２）中、Ａｒは芳香族基又はヘテロ芳香族基を表し、Ｒ¹はアルキル基、芳香族基又はアルキルオキシ基を表し、Ｒ²は水素原子又はアルキル基を表し、更にＲ²はＡｒと結合し環を形成してもよい。）

(In the formulas (1) and (2), Ar represents an aromatic group or a heteroaromatic group, R ¹ represents an alkyl group, an aromatic group or an alkyloxy group, and R ² represents a hydrogen atom or an alkyl group. And R ² may be bonded to Ar to form a ring.)

Ar represents an aromatic group or a heteroaromatic group, preferably a group obtained by removing one hydrogen atom from a benzene ring, naphthalene ring or carbazole ring, and more preferably a naphthalenyl group or carbazoyl group which forms a ring together with R ² .
R ¹ represents an alkyl group, an aromatic group or an alkyloxy group, preferably a methyl group, an ethyl group, a benzyl group, a phenyl group, a naphthyl group, a methoxy group or an ethoxy group, and a methyl group, an ethyl group, a phenyl group or a methoxy group Groups are more preferred.
R ² represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a substituted alkyl group, and more preferably a hydrogen atom, a substituted alkyl group that forms a ring with Ar, or a toluenethioalkyl group.

  The oxime ester compound is preferably a compound represented by the following formula (3), a compound represented by the following formula (4), or a compound represented by the following formula (5).

（式（３）〜式（５）中、Ｒ¹はアルキル基、芳香族基又はアルキルオキシ基を表し、Ｘは−ＣＨ₂−、−Ｃ₂Ｈ₄−、−Ｏ−又は−Ｓ−を表し、Ｒ³は水素原子又はハロゲン原子を表し、Ｒ⁴は水素原子、アルキル基、フェニル基、アルキル置換アミノ基、アリールチオ基、アルキルチオ基、アルコキシ基、アリールオキシ基又はハロゲン原子を表し、Ｒ⁵は水素原子、アルキル基又はアリール基を表し、Ｒ⁶はアルキル基を表す。）

(In Formula (3) to Formula (5), R ¹ represents an alkyl group, an aromatic group or an alkyloxy group, and X represents —CH ₂ —, —C ₂ H ₄ —, —O— or —S—. R ³ represents a hydrogen atom or a halogen atom, R ⁴ represents a hydrogen atom, an alkyl group, a phenyl group, an alkyl-substituted amino group, an arylthio group, an alkylthio group, an alkoxy group, an aryloxy group, or a halogen atom, R ⁵ Represents a hydrogen atom, an alkyl group or an aryl group, and R ⁶ represents an alkyl group.)

R ¹ represents an alkyl group, an aromatic group or an alkyloxy group, and has the same meaning as R ¹ in formula (1) or formula (2), and the preferred range is also the same.
R ⁴ represents a hydrogen atom, an alkyl group, a phenyl group, an alkyl-substituted amino group, an arylthio group, an alkylthio group, an alkoxy group, an aryloxy group or a halogen atom, and represents a hydrogen atom, an alkyl group, a phenyl group, an arylthio group or a halogen atom. Are preferred, a hydrogen atom, an alkyl group, an arylthio group or a halogen atom is more preferred, and a hydrogen atom, an alkyl group or a halogen atom is still more preferred. As an alkyl group, a C1-C5 alkyl group is preferable and a methyl group or an ethyl group is more preferable. As a halogen atom, a chlorine atom, a bromine atom, or a fluorine atom is preferable.
R ⁵ represents a hydrogen atom, an alkyl group or an aryl group, and an alkyl group is preferable. As an alkyl group, a C1-C5 alkyl group is preferable and a methyl group or an ethyl group is more preferable.
R ⁶ represents an alkyl group, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.

  Below, the example of the oxime ester compound preferably used by this invention is shown. However, it goes without saying that the oxime ester compounds used in the present invention are not limited to these. In the following chemical formulae, Me represents a methyl group, and Ph represents a phenyl group.

  Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc. Japan” 42, 2924 (1969), US Pat. No. 3,905,815, and Japanese Examined Patent Publication No. 46-4605. JP, 48-34881, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP-A 62-212401, JP-A 63-70243, JP-A 63-298339, M.S. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No. 3), (1970), and particularly, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

  Examples of hexaarylbiimidazole compounds include, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, and 4,622,286. Various compounds described in the specification, specifically 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o- Bromophenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2, 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5'-tetraphenyl Imidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  A photoinitiator can be used 1 type or in combination of 2 or more types. Further, when using an initiator that does not absorb at the exposure wavelength, it is necessary to use a sensitizer.

  The total content of component B is preferably 0.5 to 30% by weight, more preferably 2 to 20% by weight, based on the total solid content in the colored photosensitive resin composition. Within this range, the sensitivity during exposure is high and the color characteristics are also good.

  In addition to the photopolymerization initiator, a photosensitizer can also be added to the composition of the present invention. Typical sensitizers used in the present invention include those disclosed in Crivello [JV Crivello, Adv. In Polymer Sci, 62, 1 (1984)], specifically pyrene, perylene, Acridine, thioxanthone, 2-chlorothioxanthone, benzoflavin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like can be mentioned. The photosensitizer is preferably added in a proportion of 50 to 200% by weight with respect to the photopolymerization initiator.

In addition to the photopolymerization initiator, a chain transfer agent can also be added to the composition of the present invention. Examples of the chain transfer agent used in the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercapto. Benzimidazole, N-phenylmercaptobenzimidazole, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, etc. And an aliphatic polyfunctional mercapto compound such as pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, and the like.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
The addition amount of the chain transfer agent is preferably in the range of 0.01 to 15% by weight with respect to the total solid content of the composition of the present invention, from the viewpoint of reducing sensitivity variation, and preferably 0.1 to 10 % By weight is more preferable, and 0.5 to 5% by weight is particularly preferable.

(Component C) Ethylenically unsaturated compound The colored photosensitive resin composition of the present invention contains an ethylenically unsaturated compound.
The ethylenically unsaturated compound that can be used in the present invention is a polymerizable compound having at least one ethylenically unsaturated double bond.
Examples of ethylenically unsaturated compounds include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably An ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound are used.
For example, the components described in paragraph 0011 of JP-A-2006-23696 and the components described in paragraphs 0031 to 0047 of JP-A-2006-64921 can be exemplified.

  Also suitable are urethane addition polymerizable compounds produced by the addition reaction of isocyanate and hydroxyl group, as described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Urethane acrylates such as those described above, and urethane having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 Compounds are also suitable.

  Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting with acrylic acid. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these ethylenically unsaturated compounds, the details of usage, such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the performance design of the final photosensitive material. For example, it is selected from the following viewpoints.
From the viewpoint of heat resistance and reliability, an ethylenically unsaturated compound having 3 or more functional groups, more preferably 4 or more functional groups is preferable per molecule. Furthermore, by using together a polymerizable compound having an ethylenically unsaturated bond having a different functional number and / or a different polymerizable group (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound), the mechanical properties are improved. It is also effective to adjust.
Moreover, the polymeric compound containing a carboxy group is also preferable from a viewpoint of adjustment of developability. In this case, heat resistance and reliability can be improved by crosslinking with the structural unit (a2) of Component A, which is preferable.
Furthermore, from the viewpoints of adhesion to the substrate, compatibility with the radical polymerization initiator, and the like, it is also preferable that it is a modified ethylene oxide (EO) or contains a urethane bond.

  From the above viewpoints, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate , Pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, etc., and commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), NK ester A-TMMT , NK ester A-TMPT, NK ester A-TMM-3, NK oligo UA-32P, NK oligo UA-7200 (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix M-305, Aronix -306, Aronix M-309, Aronix M-450, Aronix M-402, TO-1382 (manufactured by Toagosei Co.), V # 802 (manufactured by Osaka Organic Chemical Industry Ltd.) is preferable. Among these, dipentaerythritol hexa (meth) acrylate is particularly preferable.

  The content of Component C is preferably 5 to 60% by weight, more preferably 10 to 50% by weight, and more preferably 15 to 45% by weight based on the total solid content of the photosensitive resin composition of the present invention. % Is more preferable. Within this range, both good developability, heat resistance and reliability are achieved, and the sensitivity during exposure is also high.

(Component D) Colorant The colored photosensitive resin composition of the present invention contains (Component D) a colorant in order to form a colored pattern.
As the colorant, pigments and dyes can be appropriately selected and used.
Further, as the colorant, a pigment and / or a dye having an average primary particle size of 10 nm to 30 nm is preferable. In the above aspect, a colored photosensitive resin composition for a color filter having high brightness and high contrast can be obtained.

As the chromatic color pigment, conventionally known various inorganic pigments or organic pigments can be used, but organic pigments are preferably used from the viewpoint of reliability.
In the present invention, examples of the organic pigment include organic pigments described in paragraph 0093 of JP-A-2009-256572.
In particular,
C. I. Pigment Red 177, 224, 242, 254, 255, 264,
C. I. Pigment Yellow 138, 139, 150, 180, 185,
C. I. Pigment Orange 36, 38, 71,
C. I. Pigment Green 7, 36, 58,
C. I. Pigment Blue 15: 6,
C. I. Pigment Violet 23
Is preferable from the viewpoint of color reproducibility, but the present invention is not limited thereto.
These organic pigments can be used alone or in various combinations in order to increase color purity.

  When a pigment is used as Component D, the content in the colored photosensitive resin composition of the present invention is preferably 10 to 55% by weight with respect to the total solid content of the composition, and is preferably 15 to 50% by weight. Is more preferable. When the pigment content is within the above range, it is effective to ensure excellent color characteristics.

As the pigment used in the present invention, it is preferable to use a pigment having an average primary particle diameter of 10 nm or more and 30 nm or less. By using a pigment having an average primary particle diameter in this range, a colored photosensitive resin composition for a color filter having excellent dispersibility stability and coloring power, high luminance, and high contrast can be obtained.
The average primary particle diameter in the present invention is the longer diameter of 400 primary particles of the pigment constituting the aggregate on a two-dimensional image obtained by photographing particles in the field of view with a transmission electron microscope. The average value of the (major axis) and the shorter diameter (minor axis) is obtained and averaged.

There are no particular restrictions on the method of preparing the pigment having an average primary particle size in the range of 10 to 30 nm. Any method can be used to finely pulverize and adjust the particle size to the above range. In order to obtain pigment particles having a relatively small average primary particle diameter, it is preferable to employ a solvent salt milling process as a method for adjusting the pigment to the above average primary particle diameter.
This solvent salt milling process refers to a process of kneading and grinding a pigment, an inorganic salt, and an organic solvent. The pigment having a large particle size may be subjected to solvent salt milling after dry grinding. When kneading and grinding the pigment, depending on the pigment type, it is preferable that a pigment derivative coexists in addition to an inorganic salt and an organic solvent from the viewpoint of inhibiting crystal growth. By allowing the pigment derivative to coexist, crystal growth at the time of kneading and grinding is suppressed, and a finer pigment can be obtained as compared with the case where the pigment derivative is not included.
Specifically, a pigment, an inorganic salt, and an organic solvent that does not dissolve the pigment are charged into a kneader, and kneading and grinding are performed therein. As a kneader at this time, for example, a kneader, a mix muller, or the like can be used.

As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used. Moreover, it is more preferable to use an inorganic salt having an average particle size of 0.5 to 50 μm. Such an inorganic salt can be easily obtained by pulverizing a normal inorganic salt.
In obtaining a pigment having an average primary particle size in the range of 10 to 30 nm, it is preferable to increase the ratio of the amount of inorganic salt used to the amount of pigment used in solvent salt milling. That is, the amount of the inorganic salt used is preferably 5 to 20 parts by weight and more preferably 7 to 15 parts based on 1 part of the pigment.

As the organic solvent, an organic solvent capable of suppressing crystal growth is preferably used, and as such an organic solvent, a water-soluble organic solvent can be suitably used. For example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene Glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene group Call, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, can be used dipropylene glycol.
The amount of the water-soluble organic solvent used in this case is not particularly limited, but is preferably in the range of 0.01 to 5 parts by weight in terms of 1 part of pigment, 0.1 to 2 More preferred is the range of parts.

The pigment derivative coexisting with the inorganic salt as desired can be appropriately selected depending on the kind of pigment to be kneaded and ground, and examples thereof include quinophthalone compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, and benzimidazolone compounds. Of these, quinophthalone compounds, phthalocyanine compounds, and the like are preferable from the viewpoints of inhibiting crystal growth and hue.
The amount of the dye derivative used in this case is not particularly limited, but is preferably 1 to 20 parts and more preferably 1 to 15 parts based on 100 parts of the pigment in terms of weight. preferable.
30-150 degreeC is preferable and the temperature at the time of solvent salt milling has more preferable 50-100 degreeC. The solvent salt milling time is preferably 5 to 20 hours, and more preferably 8 to 18 hours.

Thus, a mixture containing the pigment, the inorganic salt, and the organic solvent as the main components is obtained. The organic solvent and the inorganic salt are removed from the mixture, and the solid material mainly containing the pigment is washed, filtered, if necessary. By drying, pulverizing, etc., it is possible to obtain a pigment powder that has been refined to have a specific average primary particle size.
As washing after kneading and grinding, either water washing or hot water washing can be employed. The number of washings may be repeated in the range of 1 to 5 times. In the case of the mixture using a water-soluble inorganic salt and a water-soluble organic solvent, the organic solvent and the inorganic salt are easily removed by washing with water.
Examples of the drying after filtration and washing described above include batch-type or continuous drying in which the pigment is dehydrated and / or desolvated by heating at 80 to 120 ° C. with a heating source installed in a dryer. Examples of the dryer generally include a box dryer, a band dryer, and a spray dryer.
In addition, the pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle diameter of the primary particles, but for example, in the case of drying using a box dryer or a band dryer. When the pigment is in the form of a lamp or the like, it is carried out to break the pigment into powder, and examples thereof include pulverization with a mortar, hammer mill, disk mill, pin mill, jet mill and the like.

  Further, in the present invention, it is preferable to use a pigment coated with a polymer compound in the pigment miniaturization step or dispersion step. That is, the pigment that can be used in the present invention is preferably coated with a polymer compound. Even if the pigment is refined by coating the pigment with a polymer compound, the formation of secondary aggregates is suppressed, and the coated pigment with improved dispersibility, which can be dispersed in the form of primary particles, dispersion It is possible to obtain and use a coated pigment excellent in dispersion stability in which the primary particles made stable are maintained.

  The polymer compound used for coating the pigment is not particularly limited as long as it has an adsorptive group to the pigment. For example, paragraphs 0029 to 0030 of JP-A-2008-83089 and paragraphs 0044 to 0047 of JP-A-2009-62457 are disclosed. Those disclosed in JP-A-2009-256572, paragraphs 0001 to 0090 can be preferably used.

When a pigment is used as the colorant, even when the above-described coated pigment is used, it is more preferable to disperse the pigment using at least one dispersant and use it as a pigment dispersion composition. By containing this dispersant, the dispersibility of the pigment can be improved.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, poly Nonionic surfactants such as oxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; anions such as W004, W005, W017 (manufactured by Yusho Co., Ltd.) Surfactants; EFKA-46, FKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Polymer dispersants such as Disperseide 9100 (both manufactured by San Nopco Co., Ltd.); various Solsperse dispersants such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 (Nippon Lubrizol) Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121 P-123 (manufactured by ADEKA Corporation) and Ionette S-20 (manufactured by Sanyo Chemical Industries, Ltd.), DISPERBYK 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (by Big Chemie). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer.

  Moreover, when using an organic pigment as a coloring agent, you may add a pigment derivative as needed. A pigment derivative introduced with a part having affinity with the dispersant or a polar group is adsorbed on the pigment surface, and this is used as an adsorption point of the dispersant, whereby the pigment is formed into fine colored particles in the colored photosensitive resin composition. It can be dispersed to prevent re-aggregation, and is effective in constructing a color filter having high contrast and excellent transparency.

Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent.
Specific examples of organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included.
Examples of the dye derivative include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

When using a pigment as a colorant, it is preferable to use it for preparation of a colored photosensitive resin composition as a pigment dispersion composition containing said pigment, a dispersing agent, a pigment derivative, a solvent, etc.
As content in the pigment dispersion composition of a dispersing agent, 1 to 100 weight% is preferable with respect to the weight of a pigment, and 3 to 70 weight% is more preferable. Within this range, developability can be secured while maintaining dispersibility stability.
As content in the pigment dispersion composition of a pigment derivative, 1-30 weight% is preferable with respect to the weight of a pigment, and 3-20 weight% is more preferable. Within this range, the viscosity can be kept low and the dispersion can be carried out well and the dispersion stability after the dispersion can be improved. A high contrast with good color characteristics can be achieved.

When a dye is used as the colorant, there is no particular limitation. For example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Patent No. 2592207, US Pat. No. 4,808,501, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, JP-A-8-2111599, JP-A-4-249549, JP-A-10-123316, JP-A-11 -302283, JP-A-7-286107, JP-A-2001-4823, JP-A-8-15522, JP-A-8-29771. JP-A-8-146215, JP-A-11-343437, JP-A-8-62416, JP2002-14220, JP2002-14221, JP2002-14222, JP Examples thereof include dyes described in JP 2002-14223, JP 8-302224, JP 8-73758, JP 8-179120, JP 8-151351, and the like.
Chemical structures include pyrazole azo structure, anilino azo structure, triphenyl methane structure, anthraquinone structure, anthrapyridone structure, benzylidene structure, oxonol structure, pyrazolotriazole azo structure, pyridone azo structure, pyromethene structure, cyanine structure, phenothiazine structure, pyrrolopyrazole Dyes having an azomethine structure, a xanthene structure, a phthalocyanine structure, a benzopyran structure, an indigo structure, or the like can be used.

In addition, when applied to a resist-based application in which a pattern is formed by performing water or alkali development, from the viewpoint that the binder or dye in the non-light-irradiated part can be completely removed by development, an acidic dye and / or its dye In some cases, a derivative can be suitably used.
In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof may be appropriately selected according to the purpose of use. Can do.

The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, and other components in the composition. It is selected in consideration of all required performance such as interaction with components, light resistance, heat resistance and the like.
Specific examples of the acid dye are shown below, but are not limited thereto.
For example, Acid Black 24; Acid Blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1; Acid Orange 8, 51, 56, 63, 74; acid red 1, 4, 8, 34, 37, 42, 52, 57, 80, 97, 114, 143, 145, 151, 183, 217; Acid Violet 7; Acid Yellow 17, 25, 29, 34, 42, 72, Preferred are dyes such as 76, 99, 111, 112, 114, 116, 184, 243; Acid Green 25 and derivatives of these dyes.
Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Solvent orange 45; Rhodamine B, Rhodamine 110 and other acid dyes and derivatives of these dyes are also preferably used.
A dye represented by any one of the following formulas (II) to (IX) is also suitable.

In the formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl Represents a group or a heterocyclic group.

  Specific examples of the compound represented by the formula (II) are listed below. However, the present invention is not limited to these.

The compounds represented by the formula (II) are described in U.S. Pat. Nos. 4,774,339, 5,433,896, JP-A Nos. 2001-240761, 2002-155052, No. 3614586, Aust. J. Chem, 1965, 11, 1835-1845, JH Boger et al, Heteroatom Chemistry, Vol. 1, No. 5, 389 (1990), etc. it can.
For the specific synthesis method, reference can be made to the descriptions in paragraphs 0131 to 0157 of JP-A-2008-292970.

In the formula (III), A ¹ is 5-pyrazolone, isoxazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, oxazolidinedione, pyrazolidinedione, indandione, hydroxypyridone, pyrazolopyridone, 1,2,3,4-tetrahydroquinoline-2,4-dione, 3-oxo-2,3-dihydrobenzo [d] thiophene-1,1-dioxide, and 3-dicyanomethine-2,3-dihydrobenzo [D] represents an acidic nucleus derived from a compound selected from the group consisting of thiophene-1,1-dioxide. L ¹ , L ² and L ³ represent a methine group. R ³³ and R ³⁴ each independently represents an alkyl group, an aryl group, an alkoxycarbonyl group or a hydrogen atom, and R ³⁵ represents a hydrogen atom, a methoxy group, a chlorine atom, a methyl group or a nitro group. n represents 0 or 1. However, it has at least one selected from a carboxyl group, a sulfonamide group, and a sulfamoyl group in the molecule.

  Specific examples of the compound represented by the formula (III) are listed below. However, the present invention is not limited to these.

In the formula (IV), R ⁴¹ represents a heterocyclic group, and R ⁴² represents a hydrogen atom or a substituent. R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxy A carbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group or a sulfamoyl group is represented. R ⁴³ and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , R ⁴⁷ and R ⁴⁸ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring.

In the formula (V), R ^a1 , R ^a2 , R ^a3 , R ^b1 , R ^b2 and R ^b3 each independently represent a hydrogen atom or a monovalent substituent, and R ^a2 and R ^a3 are bonded to each other. May form a 5- to 7-membered heterocyclic ring. A ² represents a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. n represents 0, 1, 2 or 3, and when n is 2 or more, a plurality of R ^b2 and R ^b3 may be the same or different.

In the formula (VI), R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represents a hydrogen atom, an optionally substituted alkyl group, an aryl group or —SO ₂ NH—R, wherein R ⁶⁵ represents It represents a hydrogen atom, an optionally substituted alkyl group, an aryl group, —SO ₃ H or —SO ₂ NH—R. R represents an alkyl group, an alkoxyalkyl group, a cyclohexyl group, a cyclohexylalkyl group, an alkoxy group, an aryl group or an alkylcarbonyloxy group. n represents 0 or an integer of 1 or more. When n is 0, at least one of R ^{61 to} R ⁶⁵ represents an aryl group having —SO ₂ NH—R as a substituent. When n is an integer of 1 or more, one or more —SO ₂ NH—R is bonded by substituting one or more arbitrary hydrogen atoms in the structure in [].

In the formula (VII), R ⁷¹ is an alkyl group having 2 to 20 carbon atoms, a cyclohexyl group having a carbon number of 2 to 12 alkyl chain, an alkyl cyclohexyl group having a carbon number of 1 to 4 alkyl chains, carbon atoms 2-12 of alkyl group having 2 to 12 carbon atoms substituted with an alkoxyl ^{group, L 71 -CO-O-L} 72 - an alkyl carboxyl alkyl groups ^{represented, L 73 -O-CO-L} 74 - Table Represents an alkyloxycarbonylalkyl group, a phenyl group substituted with an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms substituted with a phenyl group. L ⁷¹ represents an alkyl group having 2 to 12 carbon atoms, L ⁷² represents an alkylene group having 2 to 12 carbon atoms, L ⁷³ represents an alkyl group having 2 to 12 carbon atoms, and L ⁷⁴ represents carbon. An alkylene group of 2 to 12 is represented. R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group or a halogen atom.

In the formula (VIII), Z ¹ and Z ² each independently represent an oxygen atom or a sulfur atom. R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ are each independently a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with a hydroxy group, C1-C10 saturated aliphatic hydrocarbon group substituted by C1-C8 alkoxyl group, C1-C10 saturated aliphatic hydrocarbon group substituted by C1-C8 thioalkoxyl group, carbon An aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 2 to 10 carbon atoms is represented. R ⁸⁵ , R ⁸⁶ , R ⁸⁷ , R ⁸⁸ , R ⁸⁹ , R ^110a , R ^111a and R ^112a are each independently a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, carbon Represents a halogenated saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a carboxyl group, a sulfo group, a sulfamoyl group or an N-substituted sulfamoyl group, and R ^{85 to} R ⁸⁹ and R ^{110a to} R ^At least one of ^112a represents an N-substituted sulfamoyl group.

In the formula (IX), each R ⁹¹ independently represents a halogen atom or a sulfonic acid group, n represents an integer of 0 to 5, and A ³ represents any of the following (a) to (d): Represent. L represents an integer of 1 or 2. R ⁹² each independently represents a methyl group, a halogen atom, a sulfonic acid group or —SO ₂ N (R ⁹³ ) (R ⁹⁴ ); m represents an integer of 0 to 5; and R ⁹³ and R ⁹⁴ each represent Independently, it represents a hydrogen atom, a lower alkyl group or a phenyl group. At least one of R ⁹¹ and R ⁹² represents a sulfonic acid group. In the present invention, the lower alkyl group means an alkyl group having 1 to 8 carbon atoms.

When a dye is used as Component D, the content in the colored photosensitive resin composition of the present invention is preferably 10 to 55% by weight with respect to the total solid content of the composition, and is preferably 15 to 50% by weight. Is more preferable. When the content of the dye is within the above range, it is effective to ensure excellent color characteristics.
Component D may be any of a pigment alone, a dye alone, or a combination of a pigment and a dye, but it is preferable to use a pigment and a dye in combination.
When the pigment and the dye are used in combination, the content in the colored photosensitive resin composition of the present invention is preferably 10 to 55% by weight with respect to the total solid content of the composition, and 15 to 50% by weight. Is more preferable. When a pigment and a dye are used in combination, and the total amount of component D is within the above range, it is effective to secure excellent color characteristics and obtain higher reliability.

<Optional component>
In addition to the components A to D, the following additives can be added as optional components to the colored photosensitive resin composition of the present invention.

(Component E) Solvent The colored photosensitive resin composition of the present invention may contain a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution prepared by dissolving the essential components, Component A, Component B, Component C and Component D, and optional components described below in a solvent.
As the solvent used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl. Ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether Examples include acetates, esters, ketones, amides, lactones and the like. As specific examples of these solvents, reference can be made to paragraph 0062 of JP-A-2009-098616.
The solvent that can be used in the present invention may be used singly or in combination of two or more, but it is preferable to use two types together, propylene glycol monoalkyl ether acetates and other solvents In combination with propylene glycol monomethyl ether acetate and diethylene glycol ethyl methyl ether is particularly preferable.
The content of the solvent in the colored photosensitive resin composition of the present invention is 100 to 1,000 parts by weight with respect to a total of 100 parts by weight of components other than the solvent, particularly from the viewpoint of adjusting the viscosity to be suitable for slit coating. It is preferable that it is 150-850 weight part, It is still more preferable that it is 200-700 weight part.

The viscosity of the colored photosensitive resin composition of the present invention is preferably 1 to 50 mPa · s, more preferably 1 to 30 mPa · s, and most preferably 1 to 20 mPa · s.
The viscosity can be measured at 25 ± 0.2 ° C. using, for example, a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd. The rotation speed at the time of measurement is 100 rpm for less than 5 mPa · s, 50 rpm for 5 mPa · s to less than 10 mPa · s, 20 rpm for 10 mPa · s to less than 30 mPa · s, and 10 rpm for 30 mPa · s or more.

(Component F) Adhesion improving agent The colored photosensitive resin composition of the present invention may contain an adhesion improving agent.
The adhesion improver is a compound that improves the adhesion between a cured film and an inorganic substance serving as a substrate, for example, a silicon compound such as glass, silicon, silicon oxide, or silicon nitride, gold, copper, aluminum, or the like. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as the adhesion improving agent is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
As the silane coupling agent, the silane coupling agent described in paragraph 0048 of JP-A-2009-98616 is preferable, and γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, More preferred is γ-glycidoxypropyltrialkoxysilane. These can be used alone or in combination of two or more. These are also effective for adjusting the taper angle with the substrate.
The content of the adhesion improving agent in the colored photosensitive resin composition of the present invention is 0.1 with respect to the total of the components including the adhesion improving agent other than the solvent, that is, the total solid content of the colored photosensitive resin composition. -20% by weight is preferable, and 0.2-5% by weight is more preferable.

(Component G) Polymerization inhibitor The colored photosensitive resin composition of the present invention may contain a polymerization inhibitor.
The polymerization inhibitor means hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation to radicals or other polymerization initiation species generated in the colored photosensitive resin composition by light or heat ( Or a substance that plays a role of suppressing the initiation of polymerization unintentionally by deactivating the polymerization initiation species. The polymerization inhibitors described in paragraphs 0154 to 0173 of JP 2007-334322 A can be used.
Among these, p-methoxyphenol is preferably exemplified as the polymerization inhibitor.
The content of the polymerization inhibitor in the colored photosensitive resin composition of the present invention is preferably 0.0001 to 5% by weight, more preferably 0.001 to 5% by weight, based on the total weight of the ethylenically unsaturated compound. 0.001 to 1% by weight is particularly preferable.

(Component H) Surfactant The colored photosensitive resin composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. Specific examples include nonionic surfactants described in paragraph 0058 of JP-A-2009-098616, and among these, fluorosurfactants are preferable. These surfactants can be used individually by 1 type or in mixture of 2 or more types.
Further, as the surfactant, the structural unit A and the structural unit B represented by the following formula (1) are included, and the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography using THF as a solvent is 1, A copolymer having a molecular weight of 000 or more and 10,000 or less can be given as a preferred example.

（式（１）中、Ｒ¹及びＲ³はそれぞれ独立に、水素原子又はメチル基を表し、Ｒ²は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ⁴は水素原子又は炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐ及びｑは重合比を表す重量百分率であり、ｐは１０重量％以上８０重量％以下の数値を表し、ｑは２０重量％以上９０重量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｎは１以上１０以下の整数を表す。）

(In the formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or carbon number. 1 represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages representing a polymerization ratio, and p is a numerical value of 10% to 80% by weight. Q represents a numerical value of 20 wt% or more and 90 wt% or less, r represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less.)

The L is preferably a branched alkylene group represented by the following formula (2). R ⁵ in the formula (2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. More preferred is an alkyl group of 3. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by weight.

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
The addition amount of the surfactant in the colored photosensitive resin composition of the present invention is preferably 0.01 to 1.0% by weight with respect to 100% by weight of the total components other than the solvent, and is 0.02 to 0.02%. 7% by weight is particularly preferred. Within this range, the coatability and the uniformity of the cured film are good.

  Examples of surfactants that can be used in the present invention include, for example, commercially available products such as MegaFuck F142D, F172, F173, F176, F177, F183, F479, F482, F554, F780, F781, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Corporation), Florard FC-135, FC-170C, FC- 430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, C-106 (Asahi Glass Co., Ltd.), EFTOP EF351, the 352, the 801, the 802 (manufactured by Mitsubishi Materials Electronic Chemicals Co.), and the like.

(Component I) Crosslinking agent A crosslinking agent is added to the colored photosensitive resin composition of the present invention as necessary.
Examples of the crosslinking agent include compounds having two or more epoxy groups or oxetanyl groups in the molecule, and alkoxymethyl group-containing crosslinking agents. By adding a crosslinking agent, the cured film can be made a strong film.

As a crosslinking agent, a polyfunctional epoxy compound etc. can be mentioned, for example.
Examples of the polyfunctional epoxy compound that can be used in the present invention include bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound.
For example, as bisphenol A type epoxy compounds, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. (Manufactured by Tohto Kasei Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103, etc. Other than these, the similar bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as EBECRYL 3700, 3701, and 600 (manufactured by Daicel UC Corporation) can also be used.
Examples of the cresol novolac type epoxy compound include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704 and the like (manufactured by Tohto Kasei Co., Ltd.), Epicron N-660, N-670, N- 680, N-690, N-695, YDCN-704L (manufactured by DIC Corporation), Denacol EM-125, etc. (manufactured by Nagase ChemteX Corporation), 3,5,3 'as biphenyl type epoxy compounds , 5'-tetramethyl-4,4'-diglycidylbiphenyl, and the like.
Examples of the alicyclic epoxy compound include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.), Santo Tote ST. -3000, ST-4000, ST-5080, ST-5100, and the like (manufactured by Toto Kasei Co., Ltd.). In addition, Epototo YH-434 and YH-434L which are amine type epoxy resins, glycidyl ester in which dimer acid is modified in the skeleton of bisphenol A type epoxy resin, and the like can be used.

  Among these epoxy resins, novolak type epoxy compounds and alicyclic epoxy compounds are preferable, and those having an epoxy equivalent of 180 to 250 are particularly preferable. As such materials, Epicron N-660, N-670, N-680, N-690, N-695, YDCN-704L (above DIC Corporation), EHPE3150 (Daicel Chemical Industries, Ltd.) Can be mentioned.

In the composition of this invention, you may contain 2 or more types of polyfunctional epoxy compounds.
From the viewpoint of obtaining excellent heat resistance, solvent resistance and hardness of the cured film, the content of the polyfunctional epoxy compound that can be used in the present invention in the colored photosensitive resin composition is a component other than the solvent. 0 to 20% by weight is preferable with respect to the total of 100% by weight, and more preferably 1 to 10% by weight. When the content is within the above range, the solvent resistance of the film can be effectively improved.

<Other ingredients>
If necessary, other components such as a plasticizer, a thermal radical generator, a development accelerator, and an antioxidant can be added to the colored photosensitive resin composition of the present invention. As these components, for example, those described in JP2009-098616A, JP2009-244801A, and other known ones can be used. In addition, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, etc. may be added to the colored photosensitive resin composition of the present invention. Good.

II. Manufacturing method of color filter for display device The colored photosensitive resin composition and the pattern forming method of the present invention are suitable for a color filter for a display device. Hereinafter, the pattern forming method of the present invention will be described as a colored pattern forming composition and a forming method in a method for producing a color filter for a liquid crystal display device, but the present invention is not limited to this method.
The color filter of the present invention is produced by forming a colored pattern on the light-transmitting substrate using the colored photosensitive resin composition of the present invention, but further steps can be provided as necessary. .

The colored pattern (cured film) forming method of the present invention includes a film forming step of forming a film on a substrate with the colored photosensitive resin composition of the present invention, an exposure step of exposing the film with actinic rays, and the exposed It is preferable to include a development step of developing the film with an aqueous developer and a post-baking step of heat-treating the developed film.
Moreover, in the said film formation process, it is preferable to use a solvent for the colored photosensitive resin composition of this invention, and the said film formation process apply | coated the colored photosensitive resin composition of this invention on a board | substrate. More preferably, it is a solvent removal step of removing the solvent from the applied colored photosensitive resin composition.
That is, the colored pattern (cured film) forming method of the present invention more preferably includes the following steps (1) to (5).
(1) Application step of applying the colored photosensitive resin composition of the present invention onto a substrate (2) Solvent removal step of removing a solvent from the applied colored photosensitive resin composition to form a film (3) Application (4) Development process for developing the exposed film with an aqueous developer (5) Post-baking process for heat-treating the developed film Each process will be described in order below. To do.

In the coating step (1), it is preferable to apply the colored photosensitive resin composition of the present invention on a substrate to form a wet film containing a solvent.
In the solvent removal step (2), it is preferable to remove the solvent from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate.
In the exposure step (3), it is preferable to irradiate the obtained coating film with an actinic ray having a wavelength of 300 nm to 450 nm.

In the developing step (4), development is performed using an alkaline developer. It is preferable to form a negative image by removing the unexposed areas that are not cured.
In the post-baking step of (5), by heating the obtained negative image, the acetal or ketal in component A is pyrolyzed to produce a carboxy group or a phenol, and crosslinked with an epoxy group and / or an oxetanyl group. Thus, a stronger cured film can be formed. This heating is preferably performed at a high temperature of 150 ° C. or more, more preferably 180 to 250 ° C., and particularly preferably 200 to 250 ° C. The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 10 to 90 minutes.
Before the post-baking step, the entire surface of the development pattern can be irradiated with actinic rays, preferably ultraviolet rays.
Next, the formation method of the coloring pattern using the colored photosensitive resin composition of this invention is demonstrated concretely.

<Preparation method of colored photosensitive resin composition>
The essential components of component A to component D are mixed at a predetermined ratio and by any method, and dissolved by stirring to prepare a colored photosensitive resin composition. For example, it is possible to prepare a resin composition by preparing components A to D in a solution in which each of them is previously dissolved in a solvent and then mixing them in a predetermined ratio. The composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

<Coating process and solvent removal process>
A desired dry coating film can be formed by applying the colored photosensitive resin composition of the present invention to a predetermined substrate and removing the solvent by reducing pressure and / or heating (prebaking). As the substrate, for example, in the production of a liquid crystal display element, a light-transmitting substrate such as non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and a transparent conductive film attached thereto is used. In the production of a solid-state imaging device, a photoelectric conversion device substrate and the like are mentioned. Furthermore, a plastic substrate is also possible. In these substrates, a black matrix is formed in a lattice shape, a stripe shape, or the like, and a colored pattern is formed in an empty portion of the lattice or stripe.
Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.
(1) The method of the application | coating process to a board | substrate is not specifically limited, For example, methods, such as a slit coat method, a spray method, a roll coat method, a spin coat method, can be used. Among these, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Here, the large substrate means a substrate having a size of 1 m or more and 5 m or less on each side. Moreover, (2) The heating conditions of the solvent removal step are preferably about 80 to 130 ° C. and about 30 to 120 seconds.

  The (dry) film thickness of the colored photosensitive resin composition layer is formed to be 0.5 to 4.0 μm in order to obtain a sufficient color reproduction region and sufficient panel luminance. It is preferable that the thickness is 1.0 to 3.5 μm.

<Exposure process>
(3) In the exposure step, the substrate provided with the coating film is irradiated with actinic rays in a predetermined pattern. Actinic rays having a wavelength of 300 nm to 450 nm can be preferably used.
For exposure with actinic rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a laser generator, or the like can be used.
When a mercury lamp is used, actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used.

  Further, in an exposure method using a laser generator, an ultraviolet laser is used as a light source. Laser is an acronym for Light Amplification by Stimulated Emission of Radiation in English. Oscillators and amplifiers that produce monochromatic light with stronger coherence and directivity by amplification and oscillation of light waves, utilizing the phenomenon of stimulated emission that occurs in materials with inversion distribution, crystals, glass, liquids, dyes as excitation media, There are gases and the like, and lasers having an oscillation wavelength for known ultraviolet light such as solid laser, liquid laser, gas laser, and semiconductor laser can be used from these media. Among these, a solid laser and a gas laser are preferable from the viewpoint of laser output and oscillation wavelength.

As a wavelength that can be used in the present invention, an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm is preferable, and an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm is preferably used for the photosensitive of the colored photosensitive resin composition. It is more preferable in that it matches the wavelength.
Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. .
The exposure amount is preferably in the range of 1 to 500 mJ / cm ^2, the range of 1 to 100 mJ / cm ² is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

There are no particular restrictions on the apparatus that can be used in the present invention, but commercially available devices include Calisto (buoy technology), AEGIS (buoy technology), and DF2200G (Dainippon Screen). Manufactured by Manufacture Co., Ltd. can be used, and devices other than those described above are also preferably used.
In addition, a light emitting diode (LED) and a laser diode (LD) can be used as an exposure source. In particular, ultraviolet LED and ultraviolet LD are suitable. For example, Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. If even shorter wavelengths are required, US Pat. No. 6,084,250 discloses an LED that can emit actinic radiation centered between 300 nm and 370 nm. Other ultraviolet LEDs are also available and can be irradiated with actinic rays in different ultraviolet bands. A particularly preferable exposure source in the present invention is a UV-LED, and a UV-LED having a peak wavelength at 340 to 370 nm is most preferable.

  (3) In the exposure step, pattern exposure may be performed through a predetermined mask, or exposure may be performed in a pattern with the exposure light focused. From the viewpoint of productivity, it is preferable to perform exposure using a mask.

<Development process>
(4) In the developing step, the uncured part after exposure is eluted in the developer, and only the cured part remains.
Any developer can be used as long as it dissolves the colored photosensitive resin composition film in the uncured part while not dissolving the cured part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
As said organic solvent, what was enumerated as the above-mentioned solvent which can be used when preparing a pigment dispersion composition or the coloring photosensitive resin composition of this invention is mentioned.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentrations of alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene are preferably 0.001 to 10% by weight, more preferably 0. An alkaline aqueous solution dissolved so as to be 0.01 to 1% by weight is exemplified.
In addition, when alkaline aqueous solution is used as a developing solution, generally washing | cleaning (rinsing) with water is performed after image development.

The development temperature is preferably 20 ° C to 35 ° C, and more preferably 23 ° C to 30 ° C.
The development time is preferably 10 to 100 seconds, and more preferably 20 to 80 seconds.
The shower pressure is preferably 0.01 to 0.5 MPa, more preferably 0.05 to 0.3 MPa, and still more preferably 0.1 to 0.3 MPa.
By selecting these conditions, it is possible to arbitrarily design the pattern shape to be rectangular or forward tapered.

<Post-bake process>
(5) In the post-bake process, the pattern corresponding to the exposure region obtained by development is heated at a predetermined temperature, for example, 180 ° C. to 250 ° C. for a predetermined time, for example, using a heating device such as a hot plate or oven. Heat treatment is performed for 5 to 60 minutes on a hot plate, and 30 to 90 minutes for an oven, thereby decomposing the acetal or ketal in Component A to generate a carboxy group and / or a phenolic hydroxyl group. By crosslinking with the functional group, a color filter having excellent reliability can be formed.

  When forming a colored pattern of RGB three hues, the formation, exposure, development, and baking cycles of the photosensitive resin composition layer may be repeated for the desired number of hues, or the photosensitive resin for each hue. After the formation, exposure, and development of the composition layer, all the hues may be combined and post-baked. As a result, a color filter including colored pixels having a desired hue is produced.

Moreover, the cured film of this invention is a cured film obtained by hardening | curing the colored photosensitive resin composition of this invention, and it is preferable that it is a cured film obtained by the formation method of the said cured film.
With the colored photosensitive resin composition of the present invention, a cured film excellent in various reliability and excellent in color characteristics even when baked at a high temperature can be obtained. The color filter using the colored photosensitive resin composition of the present invention is useful for applications of organic EL display devices and liquid crystal display devices, and particularly useful for applications of liquid crystal display devices.
The organic EL display device or the liquid crystal display device of the present invention is not particularly limited except that it has a color filter formed using the colored photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device and a liquid crystal display device.

III. Liquid crystal display device The color filter for a display device produced by the colored pattern forming method of the present invention is suitable for production of a liquid crystal display device, and the liquid crystal display device using the color filter can display a high-quality image. it can.
For the definition of display devices and explanation of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Devices (Junaki Ibuki, Sangyo Tosho) Issued in 1989). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described, for example, in “Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)”. Furthermore, the present invention is a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, IPS, OCS, FFS, and R-OCB. It can also be applied to.
Further, the color filter of the present invention is particularly suitable for a bright and high-definition COA (Color-filter On Array) system because it is excellent in reliability such as heat resistance, light resistance and solvent resistance. In the COA type liquid crystal display device, the required characteristics for the color filter layer include the required characteristics for the interlayer insulating film in addition to the normal required characteristics as described above, that is, reliability such as low dielectric constant and resistance to stripping liquid. is necessary. In the color filter of the present invention, in the post-baking step, the acetal or ketal in Component A is thermally decomposed to generate a carboxy group or a phenol, and is crosslinked with an epoxy group and / or an oxetanyl group to form a stronger cured film. Since it can be formed, it is highly reliable and useful for a COA liquid crystal display device.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(Toray Research Center, Inc., research and research division, issued in 2001)". .

The liquid crystal display device of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members.
Regarding these materials, for example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC Co., Ltd., published in 1994)”, “Current Status and Future Prospects of the 2003 Liquid Crystal Related Market (Volume 2) (Table Yoshiyoshi, Fuji Chimera Research Institute, Inc., published in 2003) ”.
Regarding backlights, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Have been described.

  When the color filter of the present invention is used in a liquid crystal display device, high brightness and high contrast can be realized when combined with a conventionally known three-wavelength cold-cathode tube, but red, green, and blue LED light sources (RGB) -LED) as a backlight can provide a liquid crystal display device with higher luminance and high color purity and good color reproducibility.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.

  (Component A) used in Examples and Comparative Examples: constitutional unit (a1) having a residue in which a carboxyl group and / or a phenolic hydroxyl group is protected by a thermally decomposable group, a constitution having an epoxy group and / or an oxetanyl group A copolymer comprising at least a unit (a2) and a structural unit (a3) having a carboxyl group and / or a phenolic hydroxyl group, (component A ′) other copolymer, (component B) radiation-sensitive radical polymerization Initiator, (component C) ethylenically unsaturated compound, (component D) colorant, (component F) adhesion improver, (component G) polymerization inhibitor, (component H) surfactant, (component I) crosslinker Is as follows.

(Component A, Component A ′)
<Synthesis of Copolymer A-1>
To 144.2 parts (2 molar equivalents) of ethyl vinyl ether, 0.5 part of phenothiazine was added, and 86.1 parts (1 molar equivalent) of methacrylic acid was added dropwise while cooling the reaction system to 10 ° C. or lower. ) For 4 hours. After adding 5.0 parts of pyridinium p-toluenesulfonate, the mixture was stirred at room temperature for 2 hours and allowed to stand overnight at room temperature. To the reaction solution, 5 parts of sodium bicarbonate and 5 parts of sodium sulfate were added, and the mixture was stirred at room temperature for 1 hour. Insoluble matter was filtered and concentrated under reduced pressure at 40 ° C. or lower, and the yellow oily residue was distilled under reduced pressure to obtain a boiling point (bp .) 134.0 parts of 1-ethoxyethyl methacrylate in the 43-45 ° C./7 mmHg fraction were obtained as a colorless oil.
1-Ethoxyethyl methacrylate (42 parts (0.36 molar equivalent)), methacrylic acid (13 parts (0.21 molar equivalent)), glycidyl methacrylate (GMA) (32 parts (0.30 molar equivalent)) ), 2-hydroxyethyl methacrylate (13 parts, (0.13 mole equivalent)) and propylene glycol monomethyl ether acetate (PGMEA) (132.5 parts) were heated to 70 ° C. under a nitrogen stream. While stirring the mixed solution, radical polymerization initiator V-65 (2,2′-azobis (2,4-dimethylvaleronitrile), Wako Pure Chemical Industries, Ltd., 12.4 parts) and PGMEA (100 0.0 part) was added dropwise over 2.5 hours. After completion of the dropwise addition, a PGMEA solution of copolymer A-1 (solid content concentration: 40% by weight) was obtained by reacting at 70 ° C. for 4 hours. The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the obtained copolymer A-1 was 20,000.

<Synthesis of Copolymers A-2 to A-13 and A′-1 to A′-5>
Copolymers A-2 to A-13 and A′-1 to A′— were the same as the synthesis of copolymer A-1, except that the monomer species and the amount used thereof were changed to those shown in Table 1. 5 were synthesized respectively. The addition amount of the radical polymerization initiator V-65 was adjusted to have the molecular weight shown in Table 1.

In addition, the copolymerization ratio of Table 1 is a molar ratio, and the symbol in Table 1 is as follows.
MAEVE: 1-ethoxyethyl methacrylate, MATHF: tetrahydrofuran-2-yl methacrylate

<Synthesis of Tetrahydrofuran-2-yl Methacrylate (MATHF)>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated aqueous sodium hydrogen carbonate solution (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a yellow oily residue. Was distilled under reduced pressure to obtain 125 g of tetrahydrofuran-2-yl methacrylate (MATHF) as a colorless oily substance having a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg (yield 80%).

GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
OXE-30: Methacrylic acid (3-ethyloxetane-3-yl) methyl (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
ECHMMA: 3,4-epoxycyclohexylmethyl methacrylate (CYCLOMER M100, manufactured by Daicel Chemical Industries, Ltd.)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
HEMA: 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
DCPM: Dicyclopentanyl methacrylate (FA-513M, manufactured by Hitachi Chemical Co., Ltd.)
BZMA: benzyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

(Component A ′) Other copolymer (A′-6) Propylene glycol monomethyl ether acetate (PGMEA) of copolymer of benzyl methacrylate and methacrylic acid (molar ratio = 70/30, weight average molecular weight = 5,000) ) Solution (solid content 40% by weight)
(A′-7) propylene glycol monomethyl ether acetate (PGMEA) solution of allyl methacrylate / methacrylic acid copolymer (molar ratio = 80/20) (solid content 40 wt%)
(A′-8) Cyclomer P ACA230AA (manufactured by Daicel Chemical Industries, Ltd., solid content 40% by weight)

(Component B)
(B-1) PI-1: IRGACURE OXE-01 (manufactured by BASF)
(B-2) PI-6: Carbazoyl carbooxime acetyl ester (B-3) PI-10: 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (Hodogaya Chemical Co., Ltd.)
PI-1 and PI-6 are compounds having the same structure as described above, and PI-10 is a compound shown below.

(Component C)
(C-1) KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

(Component D)
1. Pigment Dispersion Liquid Details of the polymer 1 and the polymer 2 used for the coated pigments 1 to 6 used in Examples and Comparative Examples are shown below.

<Synthesis of Polymer 1>
Monomer 1 (the following structure) 27.0 parts, methyl methacrylate 126.0 parts, methacrylic acid 27.0 parts and 1-methoxy-2-propanol 420.0 parts were introduced into a nitrogen-substituted three-necked flask. The mixture was stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three One Motor), heated while flowing nitrogen into the flask, and heated to 90 ° C. 1.69 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., V-65) was added thereto, and the mixture was heated and stirred at 90 ° C. for 2 hours. After 2 hours, 1.69 parts of V-65 was further added, and after heating and stirring for 3 hours, a 30 wt% solution of polymer 1 was obtained. As a result of measuring the weight average molecular weight of the obtained polymer 1 by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 20,000. Moreover, the acid value per solid content of the 30 weight% solution of the polymer 1 was 98 mgKOH / g from the titration using sodium hydroxide.

<Synthesis of Polymer 2>
Monomer 2 (the following structure) 27.0 parts, methyl methacrylate 126.0 parts, methacrylic acid 27.0 parts and 1-methoxy-2-propanol 420.0 parts were introduced into a nitrogen-substituted three-necked flask and stirred. The mixture was stirred with a machine (Shinto Kagaku Co., Ltd .: Three-One Motor), heated to 90 ° C. while flowing nitrogen into the flask. To this, 1.80 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., V-65) was added and stirred at 90 ° C. for 2 hours. After 2 hours, 1.80 parts of V-65 was further added, and after heating and stirring for 3 hours, a 30 wt% solution of polymer 2 was obtained. It was 21,000 as a result of measuring the weight average molecular weight of the obtained polymer 2 by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance. Moreover, the acid value per solid content of the 30 weight% solution of the polymer 2 was 99 mgKOH / g from the titration using sodium hydroxide.

  Details of the coated pigments 1 to 7 used for preparing the pigment dispersions used in Examples and Comparative Examples are shown below.

<Preparation of coated pigment 1>
Pigment (CI Pigment Red 254, manufactured by Ciba Specialty Chemicals, CROMOPHTAL RED BP) 50 parts, sodium chloride 500 parts, 20 parts of the above polymer 1 solution, and diethylene glycol 100 parts were made of stainless steel kneader ( (Made by Inoue Seisakusho Co., Ltd.) and kneaded for 9 hours. Next, this mixture was put into about 3,000 parts of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, and dried to prepare coated pigment 1.

<Preparation of coated pigment 2>
In the preparation of the coated pigment 1, C.I. I. Instead of Pigment Red 254, C.I. I. The coated pigment 2 was prepared in the same manner as the coated pigment 1 except that Pigment Red 177 (Ciba Specialty Chemicals, CROMOPHTAL RED A2B) was used.

<Preparation of coated pigment 3>
In the preparation of the coated pigment 1, C.I. I. Instead of Pigment Red 254, C.I. I. Pigment Green 36 (manufactured by Nippon Lubrizol Co., Ltd., Monastral Green 6Y-CL), polymer 2 instead of polymer 1, Pigment 3 was prepared.

<Preparation of coated pigment 4>
In the preparation of the coated pigment 1, C.I. I. Instead of Pigment Red 254, C.I. I. The coated pigment 4 was prepared in the same manner as the coated pigment 1 except that Pigment Blue 15: 6 was used.

<Preparation of coated pigment 5>
In the preparation of the coated pigment 1, C.I. I. In place of Pigment Red 254, Yellow Pigment E4GN-GT (manufactured by LANXESS) is used, Polymer 2 is used in place of Polymer 1, and the others are the same as in the preparation of Covered Pigment 1, and the coated pigment is used. 5 was prepared.

<Preparation of coated pigment 6>
In the preparation of the coated pigment 1, C.I. I. Instead of Pigment Red 254, C.I. I. The coated pigment 6 was prepared in the same manner as the coated pigment 1 except that Pigment Violet 23 was used.

<Preparation of coated pigment 7>
In the preparation of the coated pigment 1, C.I. I. Instead of Pigment Red 254, C.I. I. The coated pigment 7 was prepared in the same manner as the coated pigment 1 except that Pigment Yellow 138 was used, and the polymer 2 was used instead of the polymer 1.

  Details of pigment dispersions D-1-1-1 to D-1-8 used in Examples and Comparative Examples are shown below.

<Preparation of pigment dispersion D-1-1>
With a composition of 56 parts of coated pigment 1, 29 parts of DISPERBYK161 (manufactured by BYK-CHEMIE) as a dispersant, and 340 parts of solvent: propylene glycol monomethyl ether acetate, the number of revolutions was 3,000 r.p. using a homogenizer. p. m. The mixture is stirred for 3 hours to prepare a mixed solution, and further subjected to a dispersion treatment for 6 hours by a bead disperser Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) using 0.1 mmφ zirconia beads, and a pigment dispersion D-1-1 was prepared.

<Preparation of pigment dispersion D-1-2>
In the preparation of the pigment dispersion D-1-1, instead of the coated pigment 1, the coated pigment 2 was used, and the others were the same as the preparation of the pigment dispersion D-1-1. 2 was prepared.

<Preparation of pigment dispersion D-1-3>
In the preparation of the pigment dispersion D-1-1, instead of the coated pigment 1, the coated pigment 3 was used, and the rest was the same as the preparation of the pigment dispersion D-1-1. 3 was prepared.

<Preparation of pigment dispersion D-1-4>
In the preparation of the pigment dispersion D-1-1, the coating pigment 5 was used in place of the coating pigment 1, and the others were the same as the preparation of the pigment dispersion D-1-1. 4 was prepared.

<Preparation of pigment dispersion D-1-5>
In the preparation of the pigment dispersion D-1-1, instead of the coated pigment 1, the coated pigment 4 and the coated pigment 6 have a weight ratio of coated pigment 4 / coated pigment 6 = 100/40, and the total amount is the pigment dispersion. A pigment dispersion D-1-5 was prepared in the same manner as in the preparation of the pigment dispersion D-1-1 using the same amount as the coated pigment 1 in the preparation of 1.

<Preparation of pigment dispersion D-1-6>
A method for synthesizing the pigment used for preparing the pigment dispersion D-1-6 and a method for preparing the dispersion using the same are shown below.

(Synthesis of zinc halide phthalocyanine pigment)
Zinc phthalocyanine was produced from phthalodinitrile and zinc chloride.
Halogenation of zinc phthalocyanine is carried out by mixing 3.1 parts of sulfuryl chloride, 3.7 parts of anhydrous aluminum chloride, 0.46 parts of sodium chloride and 1 part of zinc phthalocyanine at 40 ° C., and dropping 2.2 parts of bromine. It was. The mixture was reacted at 80 ° C. for 15 hours, and then the reaction mixture was poured into water to precipitate a partially brominated zinc phthalocyanine crude pigment. This aqueous slurry was filtered, washed with hot water at 80 ° C., and dried at 90 ° C. to obtain 2.6 parts of a purified partially brominated zinc phthalocyanine crude pigment.

1 part of this partially brominated zinc phthalocyanine crude pigment, 7 parts of crushed sodium chloride, 1.6 parts of diethylene glycol and 0.09 part of xylene were charged into a double-arm kneader and kneaded at 100 ° C. for 6 hours. After kneading, it was taken out into 100 parts of water at 80 ° C. and stirred for 1 hour, followed by filtration, washing with hot water, drying and grinding to obtain a partially brominated zinc phthalocyanine pigment.
The obtained partially brominated zinc phthalocyanine pigment has an average composition of ZnPcBr ₁₀ Cl ₄ H ₂ (Pc; phthalocyanine) and contains an average of 10 bromines in one molecule, based on halogen content analysis by mass spectrometry. there were.

[Green pigment: Preparation of zinc halide phthalocyanine dispersion]
To the high-speed disperser “TSC-6H” manufactured by Igarashi Machinery Manufacturing Co., Ltd., charged with zirconia beads having a diameter of 0.5 mm, 50 parts of the partially brominated zinc phthalocyanine pigment obtained above, the acrylic dispersant “BYK- 2001 "35 parts and propylene glycol methyl ether acetate 340 parts were charged and stirred at 2,000 rpm for 8 hours to prepare pigment dispersion D-1-6.

<Preparation of pigment dispersion D-1-7>
In the preparation of the pigment dispersion D-1-1, the coating pigment 4 was used in place of the coating pigment 1, and the others were the same as the preparation of the pigment dispersion D-1-1. 7 was prepared.

<Preparation of pigment dispersion D-1-8>
In the preparation of the pigment dispersion D-1-1, instead of the coated pigment 1, the coated pigment 7 was used, and the others were the same as the preparation of the pigment dispersion D-1-1. 8 was prepared.

2. Dye Among the dyes described in the above formulas (II) to (IX), the following (D-2-1) to (D-2-12) used in Examples and Comparative Examples are shown below.

(D-2-1) Dye: Illustrative compound III-90 of the dipyrromethene metal complex compound represented by the formula (II-3)
(D-2-2) Dye: Illustrative compound IV-A of the dipyrromethene metal complex compound represented by the formula (II-3)
(D-2-3) Dye: Specific example 46 of the compound represented by formula (III)
(D-2-4) Dye: Compound represented by the following formula (4)

(D-2-5) Dye: Compound represented by the following formula (5)

(D-2-6) Dye: Compound represented by the following formula (6)

(D-2-7) Dye: Compound represented by the following formula (7)

(D-2-8) Dye: Compound represented by the following formula (8)

(D-2-9) Dye: Compound represented by the following formula (9)

(D-2-10) Dye: Compound represented by the following formula (10)

(D-2-11) Dye: Compound represented by the following formula (11)

(D-2-12) Dye: Compound represented by the following formula (12)

(Component F) Adhesion improver (F-1) KBM-503 (3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Component G) Polymerization inhibitor (G-1) p-methoxyphenol

(Component H) Surfactant (H-1) Megafac F-554 (Fluorosurfactant, manufactured by DIC Corporation)

(Component I) Crosslinker (I-1) EHPE3150 (1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, Daicel Chemical Industries, Ltd. Made)

<Preparation of colored photosensitive resin composition CB-1>
Components of the following composition were stirred and mixed to prepare a colored photosensitive resin composition CB-1 used in the examples.
Component A: 5.8 parts A-1 Component B: 2.0 parts B-1 Photosensitizer: None Chain transfer agent: None Component C: C-1 4.9 parts Component D: D-1-7 51.0 parts · Component F: F-1 0.3 parts · Component G: G-1 0.002 parts · Component H: H-1 0.02 parts · Component I: I-10 .3 parts, solvent (component E): 11.7 parts of propylene glycol monomethyl ether acetate, solvent (component E): 24.0 parts of ethyl ethoxypropionate

<Preparation of colored photosensitive resin compositions CB-2 to 42, CG-1 to 34, and CR-1 to 6>
Components A to D shown in Table 2 and Table 3, the same components as the colored photosensitive resin composition CB-1, the same amount of components F to I and the same amount of ethyl ethoxypropionate were used, and propylene glycol monomethyl ether Colored photosensitive resin compositions CB-2 to 30 and CG-1 to 30 used in the examples were adjusted so that the solid content concentration of the colored photosensitive resin composition was 20% by weight using acetate and stirred and mixed. And CR-1 to 4, and colored photosensitive resin compositions CB-31 to 42, CG-31 to 34, and CR-5 to 6 used in Comparative Examples were prepared, respectively.
CB-15, CB-28, and CG-11 include Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) as a photosensitizer and Accelerator M (manufactured by Kawaguchi Chemical Industry Co., Ltd.) as a chain transfer agent. Was further added in the same amount as component B.

Example 1
The following evaluation was performed using the colored photosensitive resin composition CB-1.

<Evaluation of development margin>
After applying on the surface of an alkali-free glass substrate (Corning, 1737, 550 mm × 660 mm) using a slit coater (Hirata Kiko Co., Ltd., HC-6000), it is dried in a clean oven at 90 ° C. for 120 seconds. Baking was performed to form a coating film having a film thickness of 2.3 μm.
The obtained coating film was exposed at an exposure amount of 60 mJ / cm ² (illuminance 20 mW / cm ² ) at a wavelength of 365 nm through a mask having a 20.0 μm line-and-space (one-to-one) pattern. The exposed coating film was developed with a 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.) at a shower pressure of 0.20 MPa for 50 seconds, and then washed with pure water. Air dried. At this time, the optimum development time was 1.2 times the minimum development time until the unexposed portion was removed through the mask.
The time from the optimum development time until the line pattern was peeled off when further development was continued was measured and used as a development margin. A development margin of 30 seconds or more is a level that causes no problem in practical use.
A: Development margin 60 seconds or more B: Development margin 45 seconds or more and less than 60 seconds C: Development margin 30 seconds or more and less than 45 seconds D: Development margin less than 30 seconds

<Formation of pixels>
After applying on the surface of an alkali-free glass substrate (Corning, 1737, 550 mm × 660 mm) using a slit coater (Hirata Kiko Co., Ltd., HC-6000), it is dried in a clean oven at 90 ° C. for 120 seconds. Baking was performed to form a coating film having a film thickness of 2.3 μm.
The obtained coating film was exposed through a mask having a 100 μm line pattern at an exposure amount of 60 mJ / cm ² (illuminance 20 mW / cm ² ) at a wavelength of 365 nm, and the exposed coating film was subjected to alkali developer CDK- Using a 1% aqueous solution of No. 1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.), the shower pressure was 0.20 MPa, the development was performed for the optimum development time, washed with pure water, and then air-dried.
Next, heat treatment was performed at 230 ° C. for 60 minutes in an oven to produce a single color filter on the glass substrate.

<Evaluation of reliability (heat resistance)>
The substrate on which the pixels are formed is additionally baked for 60 minutes in a 220 ° C. clean oven, and the color change (ΔE ^* ab) of the monochromatic color filter before and after the additional baking is measured using a spectrophotometer MCPD manufactured by Otsuka Electronics Co., Ltd. -2000 was used for evaluation. Here, ΔE ^* ab means a color difference in the L ^* a ^* b ^* color system. The change in color difference ΔE ^* ab was evaluated.
The evaluation criteria are as follows.
A: It is 1.5 or less.
B: It is larger than 1.5 and 2.5 or less.
C: It is larger than 2.5 and 3.5 or less.
D: Greater than 3.5.

<Evaluation of reliability (solvent resistance)>
The substrate on which the pixels are formed is immersed in N-methyl-pyrrolidone at 25 ° C. for 30 minutes, and the color change (ΔE ^* ab) of the monochromatic color filter before and after immersion is measured by a spectrophotometer MCPD manufactured by Otsuka Electronics Co., Ltd. -2000 was used for evaluation. Here, ΔE ^* ab means a color difference in the L ^* a ^* b ^* color system. The change in color difference ΔE ^* ab was evaluated.
The evaluation criteria are as follows.
A: It is 1.5 or less.
B: It is larger than 1.5 and 2.5 or less.
C: It is larger than 2.5 and 3.5 or less.
D: Greater than 3.5.

<Evaluation of reliability (light resistance)>
The substrate on which the pixels were formed was irradiated with a xenon lamp 120,000 lux (lux) for 40 hours (equivalent to 4.8 million lux · h). The color change (ΔE ^* ab) of the single color filter before and after the xenon lamp irradiation was evaluated using a spectrophotometer MCPD-2000 manufactured by Otsuka Electronics Co., Ltd., and used as an index of light resistance. Here, ΔE ^* ab means a color difference in the L ^* a ^* b ^* color system.
The evaluation criteria are as follows.
A: It is 1.5 or less.
B: It is larger than 1.5 and 2.5 or less.
C: It is larger than 2.5 and 3.5 or less.
D: Greater than 3.5.

(Examples 2 to 64 and Comparative Examples 1 to 18)
Each evaluation was performed similarly to Example 1 using each of the colored photosensitive resin compositions described in Tables 4 to 6.

(Examples 65 to 67)
The colored photosensitive resin compositions CB-14, CG-3, and CR-2 were used and evaluated in the same manner as in Example 1 except that the pattern exposure was changed to the following laser exposure (in addition, the substrate) The size was adjusted appropriately).
In the same manner as in Example 1, the colored photosensitive resin composition was applied onto the substrate, dried, a predetermined photomask was set through the coating film at an interval of 150 μm, and a laser was irradiated at 20 mJ / cm ² . The laser exposure apparatus used was “AEGIS” manufactured by Buoy Technology Co., Ltd. (wavelength 355 nm, pulse width about 10 nsec), and the exposure amount was measured using “PE10B-V2” manufactured by OPHIR.

  As shown in Tables 4 to 6, the colored photosensitive resin composition of the present invention can achieve both development margin and reliability, and color characteristics are not impaired even when heat treatment is performed.

  Further, when the liquid crystal display device was assembled using the color filters produced in the examples and comparative examples, the color filter produced in the examples had less light leakage in the dark place and the image quality was improved.

Claims (12)

(Component A) a structural unit (a1) having a residue in which a carboxyl group and / or a phenolic hydroxyl group is protected by a thermally decomposable group, a structural unit (a2) having an epoxy group and / or an oxetanyl group, and a carboxyl group And / or a structural unit (a3) having at least a phenolic hydroxyl group,
(Component B) Radiation sensitive radical polymerization initiator,
(Component C) an ethylenically unsaturated compound, and
(Component D) a colorant, only including,
The colored photosensitive resin composition, wherein the structural unit (a1) is a structural unit represented by the formula (A2) .

(In Formula (A2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least ^one of R ¹ and R ² is the alkyl group or aryl group, and R ³ Represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene Represents a group.) The colored photosensitive resin composition according to claim 1, wherein the structural unit (a2) has an oxetanyl group. The colored photosensitive resin composition according to claim 1 or 2 , wherein Component B comprises at least an oxime ester compound. The colored photosensitive resin composition according to any one of claims 1 to 3 , wherein Component B comprises at least a hexaarylbiimidazole compound. The colored photosensitive resin composition of any one of Claims 1-4 in which the component D contains at least the pigment whose average primary particle diameter is the range of 10-30 nm. The colored photosensitive resin composition according to any one of claims 1 to 5 , wherein Component D comprises at least a dye. The colored photosensitive resin composition according to any one of claims 1 to 6 , which is used for laser exposure in a wavelength range of 300 to 420 nm. Cured film produced by the colored photosensitive resin composition according to any one of claims 1-7. Film forming step of forming a film on a substrate by the colored photosensitive resin composition according to any one of claim 1 to 7
An exposure step of exposing the film with actinic rays;
A developing step of developing the exposed film with an aqueous developer; and
And a post-baking step of heat-treating the developed film. A color filter comprising the cured film according to claim 8 or the cured film obtained by the production method according to claim 9 . The color filter according to claim 10 , comprising the cured film on an array. Display device comprising a color filter according to claim 10 or 11.