JP2011085697A - Colored photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition which has little residue and enables formation of a coating film and a pattern having good heat resistance. <P>SOLUTION: The colored photosensitive resin composition includes a resin (A), a polymerizable compound (B), a photopolymerization initiator (C), a colorant (E), and a solvent (G). The polymerizable compound (B) contains a polymerizable compound (B1), the content of the polymerizable compound (B1) is 0.5-20 mass% in the polymerizable compound (B), and when water is added to the polymerizable compound (B1) at 40°C, the amount of water dissolving the polymerizable compound (B1) is 25-100 pts.mass relative to 100 pts.mass of the polymerizable compound (B1). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a colored photosensitive resin composition (hereinafter sometimes abbreviated as “composition”) used in a photolithographic method (photolithography). The present invention also relates to a coating film, a pattern and a color filter obtained from the composition.

  Color filters are used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels. This color filter is generally produced by a photolithographic method using a colored photosensitive resin composition.

  In pattern development of the photolithographic method, it is desired that the residue is small. For example, Patent Document 1 discloses the use of diol-type or triol-type polyglycols in a composition containing a colorant, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent in order to reduce residues. is doing.

JP 2007-58192 A

  If a component having high water solubility is used in the composition, development residue can be reduced. However, the heat resistance of a coating film or pattern obtained from a composition containing a highly water-soluble component may be reduced. This invention was made paying attention to such a situation, The objective is to provide the coloring photosensitive resin composition which can form the coating film and pattern with few residues and favorable heat resistance. is there.

The composition of the present invention that has achieved the above-mentioned object is a colored photosensitive resin containing a resin (A), a polymerizable compound (B), a photopolymerization initiator (C), a colorant (E), and a solvent (G). A functional resin composition,
The polymerizable compound (B) contains the polymerizable compound (B1),
Content of the said polymeric compound (B1) is 0.5-20 mass% in polymeric compound (B),
When water is added to the polymerizable compound (B1) at 40 ° C., the amount of water to be dissolved is 25 to 100 parts by mass with respect to 100 parts by mass of the polymerizable compound (B1). To do.

The polymerizable compound (B) contains the polymerizable compound (B1) and the polymerizable compound (B2),
The total content of the polymerizable compound (B1) and the polymerizable compound (B2) is 95% by mass or more in the polymerizable compound (B),
When adding water to the said polymeric compound (B2) at 40 degreeC, it is preferable that the quantity of the water to melt | dissolve is less than 25 mass parts with respect to 100 mass parts of polymeric compounds (B2).

  In the following, “when water is added to compound (Z) at 40 ° C., the amount of water (part by mass) dissolved in 100 parts by mass of compound (Z)” is referred to as “water of compound (Z)”. May be abbreviated as “solubility of”.

  The colorant (E) preferably contains a dye.

  A preferred resin (A) is a structural unit derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride; and a carbon-carbon double bond (ie, an olefin). And a structural unit derived from the monomer (b) having a cyclic ether structure.

  The monomer (b) having a carbon-carbon double bond and a cyclic ether structure is preferably selected from the group consisting of a compound represented by the formula (b1-1) and a compound represented by the formula (b1-2). At least one selected. Hereinafter, the “compound represented by the formula (b1-1)” may be abbreviated as “monomer (b1-1)”. Similarly, compounds represented by other chemical formulas may be abbreviated.

In formula (b1-1) and formula (b1-2), R ¹ represents a hydrogen atom or a C _1-4 saturated aliphatic hydrocarbon group, and the hydrogen atom of the saturated aliphatic hydrocarbon group is —OH. May be substituted.
L ¹ represents a single bond or a divalent C _1-6 saturated aliphatic hydrocarbon group, and —CH ₂ — of the divalent saturated aliphatic hydrocarbon group represents —O—, —S— or —NR. ² - may be substituted with, said R ² represents a hydrogen atom or a C _1-10 saturated aliphatic hydrocarbon group.

R ¹ and L ¹ in formula (b1-1) may be the same as or different from R ¹ and L ¹ in formula (b1-2), respectively. Similarly, symbols common to other formulas in the present specification may be the same or different from each other. Further, “a divalent saturated aliphatic hydrocarbon group in which —CH ₂ — is substituted with —O—” or the like means “apparently, —CH ₂ — of a divalent saturated aliphatic hydrocarbon group is — A group obtained by, for example, synthesizing a divalent saturated aliphatic hydrocarbon group and then substituting —CH ₂ — with —O— or the like. Is not meant. Expressions such as “saturated aliphatic hydrocarbon group in which a hydrogen atom is substituted with —OH” have the same meaning.

  The dye is preferably a compound having a structure represented by the formula (E1).

In formula (E1), R ^{3 to} R ⁶ each independently represent a hydrogen atom, —R ⁸ or C _6-10 aromatic hydrocarbon group, and the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom Atom, —R ⁸ , —OH, —OR ⁸ , —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ H, —SO ₃ ⁻ , —SO ₃ M ¹ , —SO ₃ R ⁸ , or —SO ₂ It may be substituted with NR ⁹ R ¹⁰ . m1 represents 0 or 1. However, m1 being 0 means that there is no positive charge on R ⁵ and the nitrogen atom.
In the formula (E1), R ⁷ represents —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ H, —SO ₃ ⁻ , —SO ₃ M ¹ , —SO ₃ R ⁸ , or —SO ₂ NR ⁹ R. Represents ¹⁰ . n1 represents the integer of 0-5. However, n1 being 0 means that R ⁷ does not exist, and when n 1 is 2 or more, a plurality of R ⁷ may be the same or different.
R ⁸ represents a C _1-10 saturated aliphatic hydrocarbon group, and the hydrogen atom of the saturated aliphatic hydrocarbon group may be substituted with —OR ¹¹ or a halogen atom, The hydrocarbon group —CH ₂ — may be substituted with —O—, —CO—, or —NR ¹¹ —.
R ⁹ and R ¹⁰ each independently represents a hydrogen atom, a linear or branched C _1-10 saturated aliphatic hydrocarbon group, a C _3-30 alicyclic hydrocarbon group, or —Ar ¹ . And the hydrogen atom of the saturated aliphatic hydrocarbon group and alicyclic hydrocarbon group may be substituted with —OH, a halogen atom, —Ar ¹ , —CH═CH ₂ or —CH═CHR ^8. In the above saturated aliphatic hydrocarbon group and alicyclic hydrocarbon group, —CH ₂ — may be substituted with —O—, —S—, —CO—, —NH— or —NR ⁸ —. , R ⁹ and R ¹⁰ may combine with each other to form a 3- to 10-membered ring, and the hydrogen atom of the ring may be substituted with —R ⁸ , —OH or —Ar ¹ . R ⁸ has the same meaning as described above.
R ¹¹ represents a hydrogen atom or a C _1-10 saturated aliphatic hydrocarbon group, and the hydrogen atom of the saturated aliphatic hydrocarbon group may be substituted with a halogen atom, and the saturated aliphatic carbon group The —CH ₂ — of the hydrogen group may be substituted with —O— or —CO—.
Ar ¹ represents a C _6-10 aromatic hydrocarbon group or a 5- to 7-membered aromatic heterocyclic group, and the hydrogen atoms of the aromatic hydrocarbon group and aromatic heterocyclic group are: —OH, —R ⁸ , —OR ⁸ , —NO ₂ , —CH═CH ₂ , —CH═CHR ⁸ or a halogen atom may be substituted. R ⁸ has the same meaning as described above.
M ¹ represents a sodium atom or a potassium atom.

  The colorant (E) may further contain a pigment. The pigment is preferably C.I. I. Pigment Blue 15: 6.

  The present invention also provides a coating film and a pattern formed using the colored photosensitive resin composition. The pattern of the present invention is preferably formed by a photolithographic method. The present invention also provides a color filter containing at least one selected from the group consisting of the coating film and the pattern.

  If the polymerizable compound (B1) having a water solubility of 25 to 100 parts by mass is used in an amount of 0.5 to 20% by mass in the polymerizable compound (B), the development residue of the colored photosensitive resin composition is reduced. The heat resistance of the coating film and pattern obtained from this composition can be maintained well.

  The composition of the present invention contains a resin (A), a polymerizable compound (B), a photopolymerization initiator (C), a colorant (E) and a solvent (G), and optionally a polymerization initiation aid (D). And other additives (F). As long as there is no notice in particular, said each component may be used individually by 1 type, and may use 2 or more types together. Hereinafter, each component contained in the composition of this invention is demonstrated in order.

<Resin (A)>
The resin (A) is preferably a resin that is soluble in a developer (particularly an alkali developer) used in the photolithographic method, and more preferably an acidic functional group (such as a carboxy group, a phenolic hydroxyl group, or a sulfo group) ( More preferably, it is a resin having a carboxy group. A preferred resin (A) includes at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride; a monomer having a carbon-carbon double bond ( It is a copolymer of a monomer (x) different from a). As the monomer (a) and the monomer (x), one type may be used alone, or two or more types may be used in combination.

As the monomer (a), for example,
(Meth) acrylic acid, crotonic acid, cinnamic acid, o-, m-, p-vinylbenzoic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl) ], Ω-carboxypolycaprolactone mono (meth) acrylate, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept Unsaturation such as 2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene Monocarboxylic acids;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid, methyl-5-norbornene-2,3-dicarboxylic acid;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);
Etc. Among these, (meth) acrylic acid is preferable, and methacrylic acid is more preferable.

  In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  The monomer (x) different from the monomer (a) is preferably a monomer having a carbon-carbon double bond and a curable group, more preferably a carbon-carbon double bond and a cyclic ether structure. The monomer (b) which has. If the resin (A) having a curable group is used, the reliability (heat resistance, light resistance, solvent resistance, mechanical properties, etc.) of the resulting colored pattern is improved.

  The monomer (b) having a carbon-carbon double bond and a cyclic ether structure may be used alone or in combination of two or more. Examples of the monomer (b) having a cyclic ether structure include a monomer (b1) having an epoxy structure, a monomer (b2) having an oxetane structure, and a monomer (b3) having a tetrahydrofuran structure. It is done. Among these, the monomer (b1) having an epoxy structure and the monomer (b2) having an oxetane structure are preferable, and the monomer (b1) having an epoxy structure is more preferable.

The epoxy structure
(1) a structure having a monocyclic oxirane ring (hereinafter abbreviated as “aliphatic epoxy structure”), and (2) a structure in which an aliphatic hydrocarbon ring and an oxirane ring are condensed (hereinafter referred to as “alicyclic epoxy structure”). Abbreviated)
Can be classified. Furthermore, the alicyclic epoxy structure
(2-1) The aliphatic hydrocarbon ring is monocyclic (hereinafter referred to as “aliphatic monocyclic epoxy structure”), and (2-2) the aliphatic hydrocarbon ring is polycyclic. (Hereinafter abbreviated as “aliphatic polycyclic epoxy structure”)
Can be classified. Among these, an alicyclic epoxy structure is preferable, and an aliphatic polycyclic epoxy structure is more preferable.

  Examples of the monomer (b1) having an aliphatic epoxy structure include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and JP-A-7-248625. Examples thereof include compounds represented by the formula (b1-3) described in the publication.

In formula (b1-3), R ^{12 to} R ¹⁴ each independently represents a hydrogen atom or a C _1-10 alkyl group. m2 represents an integer of 1 to 5.

  Examples of the monomer (b1-3) having an aliphatic epoxy structure include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and α-methyl-o-vinylbenzyl glycidyl ether. , Α-methyl-m-vinylbenzylglycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5 -Bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2 , 3,6-Tris (glycidyloxymethyl Styrene, 3,4,5-tris (glycidyloxy) styrene, and 2,4,6-tris (glycidyloxy-methyl) styrene and the like.

  Examples of the monomer (b1) having an aliphatic monocyclic epoxy structure include 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide (registered trademark) 2000; manufactured by Daicel Chemical Industries, Ltd.), 2 , 3-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.).

  The monomer (b1) having an aliphatic polycyclic epoxy structure may have a carbon-carbon double bond in a polycyclic aliphatic hydrocarbon group, and in a side chain bonded to the ring. You may have. Examples of the polycycle include a norbornane ring and a tricyclodecane ring. Among these, a tricyclodecane ring is preferable.

  Examples of the monomer (b1) having an aliphatic polycyclic epoxy structure include epoxy norbornyl (meth) acrylate {for example, 3,4-epoxynorbornyl (meth) acrylate}, formula (b1-1) And a compound represented by the formula (b1-2).

In formula (b1-1) and formula (b1-2), R ¹ represents a hydrogen atom or a C _1-4 saturated aliphatic hydrocarbon group, and the hydrogen atom of the saturated aliphatic hydrocarbon group is —OH. May be substituted.
L ¹ represents a single bond or a divalent C _1-6 saturated aliphatic hydrocarbon group, and —CH ₂ — of the divalent saturated aliphatic hydrocarbon group represents —O—, —S— or —NR. ² - may be substituted with, said R ² represents a hydrogen atom or a C _1-10 saturated aliphatic hydrocarbon group.

Examples of the saturated aliphatic hydrocarbon group which may be substituted with the hydroxy group of R ¹ include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, hydroxymethyl Group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl Group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like. R ¹ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the divalent saturated aliphatic hydrocarbon group which may be substituted with L ¹ —O— or the like include a methylene group, an ethylene group, a propanediyl group, a methyleneoxy group (—CH ₂ —O—), ethyleneoxy Group {— (CH ₂ ) ₂ —O—}, propanediyloxy group {— (CH ₂ ) ₃ —O— etc.}, methylenesulfanediyl group (—CH ₂ —S—), ethylenesulfanediyl group { — (CH ₂ ) ₂ —S—}, propanediylsulfanediyl group {— (CH ₂ ) ₃ —S— etc.}, methyleneimino group (—CH ₂ —NH—), ethyleneimino group {— (CH ₂ ) ₂ -NH-}, a propanediylimino group {-(CH ₂ ) ₃ -NH-etc.} And the like. L ¹ is preferably a single bond, a methylene group, an ethylene group, a methyleneoxy group, an ethyleneoxy group, an ethylenesulfanediyl group, or an ethyleneimino group, and more preferably a single bond or an ethyleneoxy group.

  A monomer (b1-1) and a monomer (b1-2) may be used individually by 1 type, respectively, and may use 2 or more types together, respectively. Furthermore, you may use the mixture of a monomer (b1-1) and a monomer (b1-2). When these mixtures are used, the molar ratio of monomer (b1-1): monomer (b1-2) is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10. More preferably, it is 20:80 to 80:20.

  A preferred monomer (b1-1) is represented by any one of formulas (b1-1-1) to (b1-1-15). Among these, monomer (b1-1-1), monomer (b1-1-3), monomer (b1-1-5), monomer (b1-1-7), single amount Body (b1-1-9) and monomer (b1-1-11) to monomer (b1-1-15) are more preferable, monomer (b1-1-1), monomer ( More preferred are b1-1-7), monomer (b1-1-9), and monomer (b1-1-15).

  A preferred monomer (b1-2) is represented by any one of formulas (b1-2-1) to (b1-2-15). Among these, monomer (b1-2-1), monomer (b1-2-3), monomer (b1-2-5), monomer (b1-2-7), single amount Body (b1-2-9) and monomer (b1-2-11) to monomer (b1-2-15) are more preferable, and monomer (b1-2-1), monomer ( More preferred are b1-2-7), monomer (b1-2-9), and monomer (b1-2-15).

  Examples of the monomer (b2) having an oxetane structure include 3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxymethyloxetane, and 3-ethyl-3- (meth) acryloxy. Methyloxetane, 3-methyl-3- [1- (meth) acryloxy] methyloxetane, 3-ethyl-3- [1- (meth) acryloxy] methyloxetane, 3-methyl-3- [1- (meth) acryloxy ] Ethyl oxetane, 3-ethyl-3- [1- (meth) acryloxy] ethyl oxetane, 2-phenyl-3- (meth) acryloxymethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxymethyl oxetane 2-pentafluoroethyl-3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) Acryloxyethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3- (meth) acryloxyethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxyethyl oxetane or 2 -Pentafluoroethyl-3- (meth) acryloxyethyl oxetane, 3- (meth) acryloxy oxetane, etc. are mentioned. Among these, 3-ethyl-3- (meth) acryloxymethyl oxetane is preferable.

  Examples of the monomer (b3) having a tetrahydrofuran structure include tetrahydrofurfuryl (meth) acrylate, tetrahydrofurylmethoxyethyl (meth) acrylate, tetrahydrofurylmethoxypropyl (meth) acrylate, and the like.

  The monomer (x) may contain a monomer (c) different from the monomer (a) and the monomer (b). Examples of the monomer (c) include carboxylic acid esters having a carbon-carbon double bond, amides having a carbon-carbon double bond, and a polymerizable unsaturated bond (particularly a carbon-carbon double bond). Aromatic compounds having a heavy bond), substituted vinyl compounds, N-substituted maleimides, dienes, polycyclic unsaturated compounds, and the like. A monomer (c) may be used individually by 1 type, and may use 2 or more types together.

As the monomer (c), more specifically,
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl ( Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (sometimes referred to by the common name “dicyclopentanyl (meth) acrylate” in the art) 4-tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate, 5-tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate , Phenyl (meth) acrylate, aminoethyl (meth) acrylate, diethyl maleate, fumaric acid Ethyl, unsaturated carboxylic acid esters such as itaconic acid diethyl;
Amides having a carbon-carbon double bond such as dimethyl (meth) acrylamide and isopropyl (meth) acrylamide;
An aromatic compound having a polymerizable unsaturated bond in the side chain, such as styrene, α-methylstyrene, vinyltoluene, p-methoxystyrene;
Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile or α-chloro (meth) acrylonitrile;
Halogenated vinyl compounds such as chloroethylene, dichloroethylene, trichloroethylene, fluoroethylene, difluoroethylene, trifluoroethylene, tetrafluoroethylene;
N-substituted maleimides such as N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide;
Dienes such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2] 2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2 -Polycyclic unsaturated compounds such as ene;
Etc.

Among monomers (c), benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, styrene, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide and bicyclo [2.2.1] hept-2-ene are preferred.

  As the monomer (x), only one of the monomer (b) and the monomer (c) may be used, or both of them may be used. The monomer (x) preferably contains the monomer (b). That is, the monomer (x) is preferably only the monomer (b) or both the monomer (b) and the monomer (c), more preferably only the monomer (b). . If the copolymer containing the monomer (b) is used, the heat resistance, light resistance, solvent resistance and mechanical properties of the coating film and pattern are improved.

  When the resin (A) is a copolymer of the monomer (a) and the monomer (b), the structural unit derived from the monomer (a) among all the structural units of the copolymer is: Preferably it is 2-98 mol%, More preferably, it is 15-60 mol%, The structural unit derived from a monomer (b) becomes like this. Preferably it is 2-98 mol%, More preferably, it is 40-85 mol%. . If the ratio of the monomer (a) to the monomer (b) is within the above preferred range, the storage stability, heat resistance and mechanical strength tend to be good, and within the above preferred range. If present, the developability, the remaining film rate and the solvent resistance are further improved.

  When the resin (A) is a copolymer of the monomer (a) and the monomer (c), the structural unit derived from the monomer (a) among all the structural units of the copolymer is: Preferably it is 2 to 98 mol%, more preferably 15 to 60 mol%, and the structural unit derived from the monomer (c) is preferably 2 to 98 mol%, more preferably 40 to 85 mol%. . If the ratio of the monomer (a) and the monomer (c) is within the above preferred range, the storage stability and heat resistance tend to be good, and if within the above preferred range, Further, the developability and the remaining film rate are improved.

  When the resin (A) is a copolymer of the monomer (a), the monomer (b), and the monomer (c), the monomer (a) in all the structural units of the copolymer The derived structural unit is preferably 2-97 mol%, more preferably 20-80 mol%, and the structural unit derived from the monomer (b) is preferably 2-97 mol%, more preferably 10 The structural unit derived from the monomer (c) is preferably 1 to 96 mol%, more preferably 10 to 70 mol%. If the ratio of the monomer (a) to the monomer (c) is within the above preferred range, the storage stability, heat resistance and mechanical strength tend to be good, and within the above preferred range. For example, the developability, the remaining film rate, and the solvent resistance are further improved.

  Resin (A) is, for example, a method described in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced by polymerizing monomers with reference to the literature cited in the above. More specifically, a predetermined amount of monomer (a), monomer (b) and / or monomer (c), a polymerization initiator and a solvent are charged into a reaction vessel, and in the absence of nitrogen-substituted oxygen. The copolymer can be produced by stirring, heating and keeping warm. What is necessary is just to adjust suitably the preparation method and reaction temperature of this copolymerization, considering the production equipment, the calorific value by superposition | polymerization, etc.

  For the obtained copolymer, the solution after the reaction may be used as it is. In particular, if the solvent (G) described later is used as the polymerization solvent, it can be used as it is in the resin composition without removing the solvent from the copolymer solution after polymerization, and the production process can be simplified. Further, the copolymer solution may be concentrated or diluted. Further, a copolymer taken out as a solid (powder) by a method such as reprecipitation may be used.

  The resin (A) is further a structural unit having a 1-alkyl-1-ethenecarbonyl group {more preferably a (meth) acryloyl group} at the terminal as represented by the formula (d1) or the formula (d2) ( d) may be included. If the resin (A) containing the structural unit (d) is used, pattern adhesion, solvent resistance and sensitivity can be improved.

In formula (d1) and formula (d2), R ¹⁵ and R ¹⁶ each independently represents a hydrogen atom or a C _1-6 alkyl group (preferably a hydrogen atom or a methyl group). In addition, * mark in a formula (d1) and a formula (d2) represents the coupling | bonding position of a structural unit (d1) and a structural unit (d2), respectively. The same applies to other chemical formulas.

The structural unit (d) having a 1-alkyl-1-ethenecarbonyl group at the terminal is obtained by copolymerizing the monomer (a) and the monomer (b) and / or the monomer (c). A carboxy group or a carbonyloxycarbonyl group (carboxylic acid anhydride structure) derived from the monomer (a) can be converted into a formula (b1-4) or a formula (like the method described in JP-A-2005-189574, for example). It can be formed by adding a monomer (b1) having a carbon-carbon double bond and an epoxy structure as represented by b1-5) [in the formula (b1-4) or the formula (b1-5), R ¹⁶ has the same meaning as described above. ].

  The acid value of the resin (A) is preferably 50 to 150 (mgKOH / g), more preferably 60 to 135 (mgKOH / g), and still more preferably 70 to 135 (mgKOH / g). If it is this range, the solubility with respect to a developing solution will improve, and it will become easy to melt | dissolve an unexposed part. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of a polymer having an acidic group such as a carboxy group, and is usually determined by titration using an aqueous potassium hydroxide solution. Can be sought.

  The weight average molecular weight of the resin (A) is preferably 2,000 to 100,000 (more preferably 2,000 to 50,000, still more preferably 3,000 to 30,000). If it is this range, the applicability | paintability of a composition will be favorable and there exists a tendency for a high developing speed to be obtained, maintaining the residual film rate at the time of image development. The weight average molecular weight is determined by gel permeation chromatography using polystyrene as a standard.

  The molecular weight distribution {namely, weight average molecular weight (Mw) / number average molecular weight (Mn)} of the resin (A) is preferably 1.1 to 6.0 (more preferably 1.2 to 4.0). Within this range, the developability tends to be excellent.

  The content of the resin (A) is preferably 10 to 35% by mass (more preferably 15 to 30% by mass) with respect to the solid content of the composition; the resin (A) and the polymerizable compound (B). Preferably it is 30-85 mass% (more preferably 35-75 mass%, still more preferably 40-65 mass%) with respect to the total amount. If the content of the resin (A) is within the above range, the solubility in the developer is sufficient, and there is a tendency that development residues are hardly generated on the substrate in the non-exposed part (non-pixel part). Further, the film thickness of the exposed portion (pixel portion) hardly occurs during development, and the non-exposed portion (non-pixel portion) tends to be easily removed, and the resolution and the remaining film ratio tend to be improved.

  In the present specification and claims, the “solid content of the composition” means “the total of each component of the composition excluding the solvent”. This solid content can be measured by known means such as gas chromatography or liquid chromatography.

<Polymerizable compound (B)>
The polymerizable compound (B) is a compound that is polymerized by an active radical, an acid, or the like generated from the photopolymerization initiator (C) by light irradiation, and examples thereof include a compound having a polymerizable carbon-carbon unsaturated bond. .

  The content of the polymerizable compound (B) is preferably 7 to 65% by mass (more preferably 13 to 60% by mass, still more preferably 17 to 55% by mass) with respect to the solid content of the composition. If the content of the polymerizable compound (B) is within the above range, curing will occur sufficiently, the film thickness ratio before and after development will improve, and undercut will not easily enter the pattern, resulting in better adhesion. There is.

  One feature of the present invention is that a polymerizable compound (B1) having a water solubility of 25 to 100 parts by mass is used as a part of the polymerizable compound (B). Usually, it is considered that the development residue decreases as the solubility of water of the components contained in the composition increases. However, as a result of intensive studies by the present inventors, not only when the solubility of water of the polymerizable compound (B1) is too low (that is, when the solubility of water is less than 25 parts by mass), the water of the polymerizable compound (B1) can be used. It has been found that a residue is also generated when the solubility of is too high (that is, the solubility of water exceeds 100 parts by mass). Based on such knowledge, the present invention is characterized in that the use of the polymerizable compound (B1) having a water solubility in an appropriate range (25 to 100 parts by mass) prevents the generation of residues. To do.

  The present invention is also characterized in that the polymerizable compound (B1) having a water solubility of 25 to 100 parts by mass is used in an amount of 0.5 to 20% by mass in the polymerizable compound (B). A residue may be generated when the amount of the polymerizable compound (B1) is less than 0.5% by mass. Conversely, when the amount of the polymerizable compound (B1) exceeds 20% by mass, good heat resistance cannot be ensured. Based on such knowledge, the present invention uses a polymerizable compound (B1) having a water solubility of 25 to 100 parts by mass in an appropriate amount (0.5 to 20% by mass in the polymerizable compound (B)). Thus, it is possible to prevent generation of a residue and achieve good heat resistance.

  The solubility of water in the polymerizable compound (B1) is preferably 25 parts by mass or more and 50 parts by mass or less, more preferably 25 parts by mass or more and 30 parts by mass or less. The content of the polymerizable compound (B1) in the polymerizable compound (B) is preferably 1% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 20% by mass or less.

  Examples of the polymerizable compound (B1) having a water solubility of 25 to 100 parts by mass include a compound represented by the formula (B1-1).

  In formula (B1-1), m3, n3 and o3 each independently represent an integer of 1 to 20. However, 9 ≦ m3 + n3 + o3 ≦ 20.

  The polymerizable compound (B1) having a water solubility of 25 to 100 parts by mass is commercially available. The polymerizable compound (B1-1) is, for example, “SR502” (ethoxylated (9) trimethylolpropane triacrylate), “SR9035” (ethoxylated (15) trimethylolpropane triacrylate), “SR415” (ethoxylated ( 20) Trimethylolpropane triacrylate), available from Sartomer. The polymerizable compound (B1) can be obtained from Daicel Cytec under the trade names of “EBECRYL2000” (aliphatic urethane acrylate) and “EBECRYL12” (polyether triacrylate), for example. Among these, aliphatic urethane acrylates such as EBECRYL2000 are preferable.

  The composition of the present invention may contain a polymerizable compound (B2) having a water solubility of less than 25 parts by mass (preferably less than 5 parts by mass). The total amount of the polymerizable compound (B1) and the polymerizable compound (B2) is preferably 95% by mass or more, and more preferably 97% by mass or more in the polymerizable compound (B).

  The polymerizable compound (B2) having a water solubility of less than 25 parts by mass is preferably a compound having three or more carbon-carbon unsaturated bonds. Examples of the polymerizable compound (B2) having three or more carbon-carbon unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) acryloyl isocyanurate, and pentaerythritol tetra. (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. Among these, dipentaerythritol hexaacrylate is preferable.

<Photopolymerization initiator (C)>
As the photopolymerization initiator (C), known photopolymerization initiators such as photo radical generators (for example, acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, acylphosphine oxide compounds, oxime compounds) A compound or the like) or a photoacid generator.

  Examples of the acetophenone compounds include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). ) Butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxy-1-ethanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one And the like. Among these, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one preferable.

  Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxy). Carbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of triazine compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -[2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl]- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl)- - such as [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and the like.

  As the oxime compound, an O-acyl oxime compound is preferable. Examples of O-acyloxime compounds include 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1 , 2-dione 2-oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1-O-acetate, 1- [9-ethyl -6- (2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl) -9H-carbazol-3-yl] ethanone 1-O-acetate .

  Examples of other photo radical generators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like can be mentioned.

  Examples of the photoacid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl · Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.

  Some of the compounds listed as photo radical generators generate acids simultaneously with radicals. For example, triazine compounds are sometimes used as acid generators.

As the photopolymerization initiator (C), acetophenone compounds and oxime compounds are preferable.
The content of the photopolymerization initiator (C) is preferably 0.1 to 30 parts by mass (more preferably 1 to 20 parts by mass) with respect to 100 parts by mass in total of the resin (A) and the polymerizable compound (B). ). When the content of the photopolymerization initiator (C) is within this range, the sensitivity of the composition is improved, and the exposure time can be shortened and the productivity can be improved.

<Polymerization initiation aid (D)>
The composition of the present invention may optionally contain a polymerization initiation assistant (D). The polymerization initiation assistant (D) is usually used in combination with the photopolymerization initiator (C) and promotes polymerization initiated by the photopolymerization initiator (C). Examples of the polymerization initiation assistant (D) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and the like.

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4 ′ -Bis (ethylmethylamino) benzophenone and the like. Among these, 4,4'-bis (diethylamino) benzophenone is preferable. Moreover, you may use commercial items, such as brand name "EAB-F" (made by Hodogaya Chemical Co., Ltd.), as an amine compound.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10. -Dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

  As the thioxanthone compounds, those listed for the photopolymerization initiator (C) can be used.

  The polymerization initiation assistant (D) is preferably at least one selected from the group consisting of 4,4'-bis (diethylamino) benzophenone and 2,4-diethylthioxanthone. As a preferable combination of the photopolymerization initiator (C) and the polymerization initiation assistant (D), for example, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and 4,4 ′ -Bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 4,4'-bis (diethylamino) benzophenone, 1,2-diphenyl-2,2-dimethoxy-1-ethanone And 4,4′-bis (diethylamino) benzophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and 2,4-diethylthioxanthone, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one and 2,4-diethylthioxanthone, 1,2-diphenyl-2,2-dimethoxy-1-ethanone Include 4-diethyl thioxanthone.

  When the polymerization initiation assistant (D) is used, the amount used is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol, per 1 mol of the photopolymerization initiator (C).

<Colorant (E)>
Examples of the colorant (E) include dyes and pigments. Although both dyes and pigments are substances used for coloring, in the present specification and claims, those that dissolve in a solvent are defined as dyes, and those that do not dissolve in a solvent are defined as pigments. Any of dyes and pigments may be used alone or in combination of two or more. Moreover, you may use the combination of dye and a pigment as a coloring agent (E).

  The content of the colorant (E) is preferably 5% by mass or more (more preferably 8% by mass or more, more preferably 10% by mass or more), preferably 60% by mass or less (based on the solid content of the composition). More preferably, it is 55 mass% or less, More preferably, it is 50 mass% or less. When the content of the colorant is within the above range, the amount of the resin (A) necessary for forming a coating film or pattern having sufficient mechanical strength can be secured in the composition. Moreover, if it is in the said range, the color filter of sufficient color density can be obtained from a composition.

  The colorant (E) preferably contains a dye. As the dye, known dyes such as oil-soluble dyes, acid dyes, amine salts of acid dyes, sulfonamides of acid dyes, and the like can be used. Examples of the dye include compounds classified as dyes in the color index (published by The Society of Dyers and Colorists) (for example, CI solvent dyes, CI acid dyes, CI direct dyes, C.I. dyes). I. Modern dyes, etc.) and dyes described in dyeing notes (color dyeing company).

C. I. As a solvent dye, for example,
C. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;
C. I. Solvent red 45, 49, 125, 130;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Blue 35, 37, 59, 67;
C. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35;
Etc.
In the present specification, “CI Solvent Yellow” or the like is described only for the first dye, and only the number is described for the same dye described subsequently. The same applies to pigments.

C. I. Examples of acid dyes include C.I. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
C. I. Acid Violet 6B, 7, 9, 17, 19;
C. I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109;
Etc.

C. I. Examples of the direct dye include C.I. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;
Etc.

C. I. Examples of modern dyes include C.I. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
C. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 44, 48, 49, 53, 61, 74, 77, 83, 84;
C. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;
Etc.

  As the dye, for example, an amine salt of an acidic dye having a group represented by any one of formulas (1) to (7), and a sulfone of an acidic dye having a group represented by formula (8) or formula (9) Amide derivatives can be used. Further, the sulfonamide derivative of an acid dye may have a group represented by the formula (10) in addition to the group represented by the formula (8) or the formula (9). Examples of the acid dye include azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, and phthalocyanine dyes.

^{_{- (SO 3 -) (C}} n H 2n + 1 N + H 3) (1)
− (SO ₃ ⁻ ) {(C _n H _{2n + 1} ) ₂ N ⁺ H ₂ } (2)
^{_{- (SO 3 -) {(}} C n H 2n + 1) 3 N + H} (3)
− (SO ₃ ⁻ ) {(C _n H _{2n + 1} ) ₄ N ⁺ } (4)
^{_{- (SO 3 -) (C}} o H 2o + 1 OC p H 2p N + H 3) (5)
^{_{- (SO 3 -) {(}} C n H 2n + 1) (PhCH 2) 2 N + H} (6)
^{_{- (SO 3 -) {(}} C n H 2n + 1) Py +} (7)
—SO ₂ NH (C _n H _{2n + 1} ) (8)
—SO ₂ NH (C _o H _{2o + 1} OC _p H _2p ) (9)
-SO ₃ M (10)

In formulas (1) to (10), n represents an integer of 1 or more and 20 or less. o and p each independently represent an integer of 1 or more and 10 or less. Ph represents a phenyl group. Py ⁺ is a group represented by the formula (11). M represents a hydrogen atom or a monovalent cation.

In formula (11), q represents 0 or 1, and q being 0 means that no methyl group is present. * Mark in the formula (11) represents a binding position of Py ^+, Py ⁺ binds to the C _n H _{2n + 1} carbon atoms of the formula (7) in the coupling position.

n is preferably an integer of 1 or more and 10 or less (more preferably 8 or less). o and p are each independently preferably an integer of 1 or more and 8 or less (more preferably 6 or less). q is preferably 1. Examples of the monovalent cation of M include lithium ion, sodium ion, potassium ion, ammonium ion {eg (C ₂ H ₅ ) ₃ HN ⁺ }, and preferably sodium ion.

  The number of groups represented by any one of formula (1) to formula (7) contained in the amine salt of the acid dye is preferably 1 or more and 20 or less (more preferably 10 or less, more preferably 8 or less). is there. The number of groups represented by the formula (8) or the formula (9) contained in the sulfonamide derivative of the acid dye is preferably an integer of 1 or more and 8 or less (more preferably 6 or less, more preferably 5 or less). is there. Furthermore, the sulfonamide derivative of an acid dye may have a group represented by the formula (10), preferably 8 or less, more preferably 6 or less, and still more preferably 5 or less.

  Examples of the azo dye having a sulfonamide structure include a dye represented by the formula (E2).

In the formula (E2), R ¹⁷ represents a C _2-20 alkyl group, a C _2-12 alkyl group substituted with a cyclohexyl group, a cyclohexyl group substituted with a C _1-4 alkyl group, C _{2− 12} alkoxy C _2-12 alkyl group substituted with a group, C _1-20 alkyl substituted phenyl, C _1-20 alkyl group substituted with a phenyl group, alkylcarbonyl of formula (12) Represents an oxyalkyl group or an alkyloxycarbonylalkyl group represented by formula (13) {in formula (12) and formula (13), R ²² represents a C _2-12 alkyl group, and L ² represents C _{2- 12} represents an alkanediyl group. }.
^{-L 2 -O-CO-R 22} (12)
^{-L 2 -CO-O-R 22} (13)

In formula (E2), R ^{18 to} R ²⁰ each independently represents a hydrogen atom, a C _1-4 alkyl group, a halogen atom, a hydroxy group, a carboxy group, a carbamoyl group, or a cyano group. R ²¹ represents a C _1-4 alkyl group.

As the C _2-20 alkyl group for R ¹⁷ , ethyl group, propyl group, isopropyl group, hexyl group, nonyl group, decyl group, dodecyl group, 2-ethylhexyl group, 1,3-dimethylbutyl group, 1-methylbutyl group 1,5-dimethylhexyl group, 1,1,3,3-tetramethylbutyl group and the like. Examples of the C _2-12 alkyl group substituted with the cyclohexyl group of R ¹⁷ include a cyclohexylethyl group, a 3-cyclohexylpropyl group, and an 8-cyclohexyloctyl group. _{Examples of the} cyclohexyl group substituted with the C _1-4 alkyl group of R ¹⁷ include a 2-ethylcyclohexyl group, a 2-propylcyclohexyl group, and a 2-butylcyclohexyl group. The C _2-12 alkyl group substituted with a C _2-12 alkoxy group R ^17, 3-ethoxypropyl, 3-propoxypropyl group, 4-propoxy-butyl group, 3-methyl-hexyloxy ethyl group and 3- And (2-ethylhexyloxy) propyl group. _{Examples of} the phenyl group substituted with the C _1-20 alkyl group of R ¹⁷ include an o-isopropylphenyl group. _{Examples of} the C _1-20 alkyl group substituted with the phenyl group of R ¹⁷ include a DL-1-phenylethyl group, a benzyl group, and a 3-phenylbutyl group.

Examples of the C _2-12 alkyl group for R ²² include ethyl group, propyl group, hexyl group, nonyl group, decyl group, dodecyl group, 2-ethylhexyl group, 1,3-dimethylbutyl group, 1-methylbutyl group, 1, Examples include 5-dimethylhexyl group and 1,1,3,3-tetramethylbutyl group. _Examples of the C _2-12 alkanediyl group of L ² include an ethylene group and a hexanediyl group.

_Examples of the C _1-4 alkyl group for R ¹⁸ R ²¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, and a tert-butyl group. Examples of the halogen atom of R ¹⁸ R ²⁰ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a fluorine atom and a chlorine atom are preferable.

R ¹⁷ is preferably a C _2-10 alkyl group, more preferably a 2-ethylhexyl group. R ¹⁸ is preferably a methyl group, an ethyl group, a propyl group or a butyl group, more preferably a methyl group. R ¹⁹ is preferably a cyano group. R ²⁰ is preferably a hydroxy group. R ²¹ is preferably a methyl group, an ethyl group, a propyl group or a butyl group, more preferably a butyl group. Among the dyes (E2), a dye represented by the formula (E2-1) is preferable.

  Examples of the azo dye having a sulfonamide structure include dyes represented by formula (E3), formula (E4), or formula (E5).

  Examples of the anthraquinone dye having a sulfonamide structure include a dye represented by the formula (E6).

  Examples of the triphenylmethane dye having a sulfonamide structure include a dye represented by the formula (E7).

  Examples of the phthalocyanine dye having a sulfonamide structure include a dye represented by the formula (E8).

In formula (E8), R ^{23 to} R ²⁶ each independently represents a hydrogen atom, —SO ₂ NH (CH ₂ ) ₃ OCH (CH ₃ ) ₂ group or a sulfo group (—SO ₃ H). However, at least two of R ^{23 to} R ²⁶ are —SO ₂ NH (CH ₂ ) ₃ OCH (CH ₃ ) ₂ groups.

  A preferred dye is a compound having a structure represented by the formula (E1) (that is, a xanthene dye or a sulfonamide derivative thereof). Hereinafter, the “compound having the structure represented by the formula (E1)” may be abbreviated as “dye (E1)”. Similarly, compounds having structures represented by other formulas may be abbreviated as well. Dye (E1) may be used individually by 1 type, and may use 2 or more types together.

In formula (E1), R ^{3 to} R ⁶ each independently represent a hydrogen atom, —R ⁸ or C _6-10 aromatic hydrocarbon group, and the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom Atom, —R ⁸ , —OH, —OR ⁸ , —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ H, —SO ₃ ⁻ , —SO ₃ M ¹ , —SO ₃ R ⁸ , or —SO ₂ It may be substituted with NR ⁹ R ¹⁰ . m1 represents 0 or 1. However, m1 being 0 means that there is no positive charge on R ⁵ and the nitrogen atom.
In the formula (E1), R ⁷ represents —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ H, —SO ₃ ⁻ , —SO ₃ M ¹ , —SO ₃ R ⁸ , or —SO ₂ NR ⁹ R. Represents ¹⁰ . n1 represents the integer of 0-5. However, n1 being 0 means that R ⁷ does not exist, and when n 1 is 2 or more, a plurality of R ⁷ may be the same or different.
R ⁸ represents a C _1-10 saturated aliphatic hydrocarbon group, and the hydrogen atom of the saturated aliphatic hydrocarbon group may be substituted with —OR ¹¹ or a halogen atom, The hydrocarbon group —CH ₂ — may be substituted with —O—, —CO—, or —NR ¹¹ —.
R ⁹ and R ¹⁰ each independently represents a hydrogen atom, a linear or branched C _1-10 saturated aliphatic hydrocarbon group, a C _3-30 alicyclic hydrocarbon group, or —Ar ¹ . And the hydrogen atom of the saturated aliphatic hydrocarbon group and alicyclic hydrocarbon group may be substituted with —OH, a halogen atom, —Ar ¹ , —CH═CH ₂ or —CH═CHR ^8. In the above saturated aliphatic hydrocarbon group and alicyclic hydrocarbon group, —CH ₂ — may be substituted with —O—, —S—, —CO—, —NH— or —NR ⁸ —. , R ⁹ and R ¹⁰ may combine with each other to form a 3- to 10-membered ring, and the hydrogen atom of the ring may be substituted with —R ⁸ , —OH or —Ar ¹ . R ⁸ has the same meaning as described above.
R ¹¹ represents a hydrogen atom or a C _1-10 saturated aliphatic hydrocarbon group, and the hydrogen atom of the saturated aliphatic hydrocarbon group may be substituted with a halogen atom, and the saturated aliphatic carbon group The —CH ₂ — of the hydrogen group may be substituted with —O— or —CO—.
Ar ¹ represents a C _6-10 aromatic hydrocarbon group or a 5- to 7-membered aromatic heterocyclic group, and the hydrogen atoms of the aromatic hydrocarbon group and aromatic heterocyclic group are: —OH, —R ⁸ , —OR ⁸ , —NO ₂ , —CH═CH ₂ , —CH═CHR ⁸ or a halogen atom may be substituted. R ⁸ has the same meaning as described above.
M ¹ represents a sodium atom or a potassium atom.

  When the structure represented by the formula (E1) has a positive charge, the dye (E1) has a counter anion. The counter anion is preferably a halide ion.

Among dyes (E1),
R ^{3 to} R ⁶ in the formula (E1) each independently represent a hydrogen atom, —R ²⁸ or a C _6-10 aromatic hydrocarbon group, and the hydrogen atom of the aromatic hydrocarbon group is a halogen atom, — Substituted with R ²⁸ , —OH, —OR ²⁸ , —CO ₂ H, —CO ₂ R ²⁸ , —SO ₃ ⁻ , —SO ₃ Na, —SO ₃ H, —SO ₃ R ²⁸ , or —SO ₂ NHR ²⁹ May be;
R ^{7 in} formula (E1) represents —CO ₂ H, —CO ₂ R ²⁸ , —SO ₃ H, —SO ₃ ⁻ , —SO ₃ Na, or —SO ₂ NHR ²⁹ ;
R ²⁸ represents a C _1-10 saturated hydrocarbon group, and a hydrogen atom of the saturated hydrocarbon group may be substituted with —OR ³⁰ or a halogen atom;
R ²⁹ represents a hydrogen atom, —R ²⁸ , or a C _6-10 aromatic hydrocarbon group, and the hydrogen atom of the C _6-10 aromatic hydrocarbon group is substituted with —R ²⁸ or —OR ^28. May be;
R ³⁰ represents a C _1-10 saturated hydrocarbon group, and a hydrogen atom of the saturated hydrocarbon group may be substituted with a halogen atom;
m1 and n1 have the same meaning as described above;
Dyes are preferred.

In formula (E1), preferably at least one of R ^{3 to} R ⁶ , more preferably at least one of R ³ and R ⁴ and at least one of R ⁵ and R ⁶ is a C _1-4 alkyl group or substituted A C _6-10 aromatic hydrocarbon group which may be _substituted . More preferably, at least one of R ³ and R ⁴ and at least one of R ⁵ and R ⁶ is an optionally substituted C _6-10 aromatic hydrocarbon group.

R ⁷ in the dye (E1) is preferably -CO ₂ H, C _1-10 alkoxycarbonyl group (e.g. ethyloxycarbonyl _{group), - SO 3 H, -SO} 3 -, -SO 3 Na, N- ( C _1-10 alkyl) sulfamoyl group {eg, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group}, N- (C _7-16 aralkyl) sulfamoyl group {eg, N- ( 3-phenyl-1-methylpropyl) sulfamoyl group} or N- (C _1-10 alkoxy C _1-10 alkyl) sulfamoyl group {eg N- (3-isopropoxypropyl) sulfamoyl group, N- {3- ( 2-ethylhexyloxy) propyl} sulfamoyl group}, more preferably N- (C _1-10 alkyl) sulfamoyl group, still more preferably N- ( 1,5-dimethylhexyl) sulfamoyl group or N- (2-ethylhexyl) sulfamoyl group. N1 in the formula (E1) is preferably 1 or 2.

In the dye (E1)
R ³ and R ^{6 in} formula (E1) each independently represent a phenyl group, and the hydrogen atom of the phenyl group may be substituted with —R ²⁸ or —SO ₂ NHR ²⁹ ;
R ⁴ and R ^{5 in} formula (E1) represent a hydrogen atom;
N1 in the formula (E1) is 1, and R ⁷ is present at the 2-position and represents —SO ₃ ⁻ or —SO ₂ NHR ²⁹ ;
R ²⁸ , R ²⁹ and m1 have the same meaning as described above;
Dyes are preferred.

  In the dye (E1), a compound having a structure represented by the formula (E1-1) is preferable.

In formula (E1-1), R ^{33 to} R ³⁶ each independently represent a hydrogen atom, —R ⁸ or C _6-10 aromatic hydrocarbon group, and the hydrogen atom of the aromatic hydrocarbon group is a halogen atom Atom, —R ⁸ , —OH, —OR ⁸ , —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ H, —SO ₃ ⁻ , —SO ₃ Na, —SO ₃ R ⁸ , or —SO ₂ NR ⁹ R ¹⁰ may be substituted.
In the formula (E1-1), R ³⁷ represents a hydrogen atom, —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ ⁻ , —SO ₃ H, or —SO ₂ NR ⁹ R ¹⁰ .
In the formula (E1-1), R ³⁸ represents —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ ⁻ , —SO ₃ H, or —SO ₂ NR ⁹ R ¹⁰ .
R ⁸ , R ⁹ , R ¹⁰ and m1 have the same meaning as described above. However, m1 being 0 means that there is no positive charge on R ³⁵ and the nitrogen atom.

Dye (E1-1) R ³⁷ in is preferably a hydrogen atom, -CO ₂ H, C _1-10 alkoxycarbonyl group (e.g. ethyloxycarbonyl _{group), - SO 3 H, -SO} 3 -, -SO 3 Na, N- (C _1-10 alkyl) sulfamoyl group, N- (C _7-16 aralkyl) sulfamoyl group {eg N- (3-phenyl-1-methylpropyl) sulfamoyl group}, N- (C _1-10 An alkoxy C _1-10 alkyl) sulfamoyl group {eg N- (isopropoxypropyl) sulfamoyl group} or N- (C _1-10 alkoxy) sulfamoyl group {eg N- (2-ethylhexyloxy) sulfamoyl group}; It is more preferably a hydrogen atom, -SO ₃ H, N- (1,5- dimethyl-hexyl) sulfamoyl group, or N-(2-ethylhexyl) sulfamoyl group

Dye R ³⁸ in (E1-1) are preferably, -CO ₂ H, C _1-10 alkoxycarbonyl group (e.g. ethyloxycarbonyl _{group), - SO 3 H, -SO} 3 -, -SO 3 Na, N- (C _1-10 alkyl) sulfamoyl group, N- (C _7-16 aralkyl) sulfamoyl group {eg N- (3-phenyl-1-methylpropyl) sulfamoyl group}, N- (C _1-10 alkoxyC _1-10 alkyl) sulfamoyl group {eg N- (isopropoxypropyl) sulfamoyl group} or N- (C _1-10 alkoxy) sulfamoyl group {eg N- (2-ethylhexyloxy) sulfamoyl group}, more preferred Is —CO ₂ H, ethyloxycarbonyl group, —SO ₃ H, or N— (C _1-10 alkyl) sulfamoyl group, and N— (1,5-dimethylhexyl) A sulfamoyl group or an N- (2-ethylhexyl) sulfamoyl group.

In formula (E1-1), preferably at least one of R ^{33 to} R ³⁶ , more preferably at least one of R ³³ and R ³⁴ and at least one of R ³⁵ and R ³⁶ is a C _1-4 alkyl group. Or it is the _C6-10 aromatic hydrocarbon group which may be substituted. More preferably, at least one of R ³³ and R ³⁴ and at least one of R ³⁵ and R ³⁶ is an optionally substituted C _6-10 aromatic hydrocarbon group.

Among dyes (E1-1),
R ³³ and R ³⁶ of formula (E1-1) each independently represent a phenyl group, a hydrogen atom of the phenyl group, a halogen ^{atom, -R 28, -OR 28, -CO} 2 R 28, -SO Optionally substituted with ₃ R ²⁸ , or —SO ₂ NHR ²⁹ ;
R ³⁴ and R ^{35 in} formula (E1-1) represent a hydrogen atom;
R ^{37 in} formula (E1-1) represents a hydrogen atom, —SO ₃ ⁻ , or —SO ₂ NHR ²⁹ ;
R ^{38 in the} formula (E1-1) represents —SO ₃ ⁻ or —SO ₂ NHR ²⁹ ;
R ²⁸ , R ²⁹ and m1 have the same meaning as described above;
Dyes are preferred.

Examples of the optionally substituted C _1-10 saturated aliphatic hydrocarbon group in the dye (E1) and the dye (E1-1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, cycloheptyl group, octyl group, 2-ethylhexyl group, cyclooctyl group, nonyl group, decanyl group, tricyclodecanyl group Methoxypropyl group, ethoxypropyl group, hexyloxypropyl group, 2-ethylhexyloxypropyl group, methoxyhexyl group, ethoxypropyl group and the like.

Examples of the C _6-10 aromatic hydrocarbon group in the dye (E1) and the dye (E1-1) include a phenyl group and a naphthyl group. Examples of the _optionally substituted C _6-10 aromatic hydrocarbon group include a phenyl group, a naphthyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a hexylphenyl group, and a decanylphenyl group. Group, fluorophenyl group, chlorophenyl group, bromophenyl group, hydroxyphenyl group, methoxyphenyl group, dimethoxyphenyl group, ethoxyphenyl group, hexyloxyphenyl group, decanyloxyphenyl group, trifluoromethylphenyl and the like. Examples of the substituent contained in the C _6-10 aromatic hydrocarbon group include an ethyl group, a propyl group, a phenyl group, a dimethylphenyl group, —SO ₃ R ⁸ , —SO ₃ R ²⁸ , —SO ₂ NHR ⁹ and —SO _{2. 2} NHR ²⁹ is preferred.

  As a halogen atom in dye (E1) and dye (E1-1), a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned.

Examples of —OR ⁸ , —OR ¹¹ , —OR ²⁸ and —OR ^{30 in the} dye (E1) and the dye (E1-1) include, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, n- Examples include butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy and the like.

Examples of —CO ₂ R ⁸ and —CO ₂ R ^{28 in the} dye (E1) and the dye (E1-1) include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, and butyl. Oxycarbonyl group, isobutyloxycarbonyl group, pentyloxycarbonyl group, isopentyloxycarbonyl group, neopentyloxycarbonyl group, cyclopentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, cycloheptyloxycarbonyl Group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, cyclooctyloxycarbonyl group, nonyloxycarbonyl group, decanyloxycarbonyl group, tricyclode Aryloxycarbonyl group, methoxypropyl oxycarbonyl group, ethoxypropyl oxycarbonyl group, hexyloxy propyloxy group, 2-ethylhexyl-oxy-propyl oxycarbonyl group, and the like methoxy hexyloxy group.

Examples of —SO ₃ R ⁸ and —SO ₃ R ^{28 in the} dye (E1) and the dye (E1-1) include a methoxysulfonyl group, an ethoxysulfonyl group, a hexyloxysulfonyl group, and a decyloxysulfonyl group. .

Examples of —SO ₂ NHR ⁹ and —SO ₂ NHR ^{29 in the} dye (E1) and the dye (E1-1) include a sulfamoyl group;
N- (methyl) sulfamoyl group, N- (cyclopropylmethyl) sulfamoyl group, N- (cyclopentylmethyl) sulfamoyl group, N- (cyclohexylmethyl) sulfamoyl group, N- (1-adamantylmethyl) sulfamoyl group, N- { Trifluoromethyl) methyl} sulfamoyl group, N-{(perfluorooctyl) methyl} sulfamoyl group;
N- (ethyl) sulfamoyl group, N- (2-hydroxyethyl) sulfamoyl group, N- (2-methoxyethyl) sulfamoyl group, N- (2-ethoxyethyl) sulfamoyl group, N- (2- (2-hydroxy Ethoxy) ethyl) sulfamoyl group, N- (2-fluoroethyl) sulfamoyl group, N- (2-chloroethyl) sulfamoyl group, N- (2-bromoethyl) sulfamoyl group;
N- (propyl) sulfamoyl group, N- (isopropyl) sulfamoyl group, N- (cyclopropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N -(3-phenyl-1-methylpropyl) sulfamoyl group, N- (3-hydroxypropyl) sulfamoyl group, N- (2-hydroxypropyl) sulfamoyl group, N- (2,3-dihydroxypropyl) sulfamoyl group, N -(Methoxypropyl) sulfamoyl group {eg N- (1-methoxypropyl) sulfamoyl group}, N- (ethoxypropyl) sulfamoyl group, N- (propoxypropyl) sulfamoyl group, N- (isopropoxypropyl) sulfamoyl group, N -(1- (2-Etoki Ethoxy) propyl) sulfamoyl group, N- (3-tert-butoxypropyl) sulfamoyl group, N- (hexyloxypropyl) sulfamoyl group, N- (2-ethylhexyloxypropyl) sulfamoyl group, N- (3-fluoropropyl) Sulfamoyl group, N- (3-chloropropyl) sulfamoyl group, N- (3-bromopropyl) sulfamoyl group;
N- (butyl) sulfamoyl group, N- (isobutyl) sulfamoyl group, N- (sec-butyl) sulfamoyl group, N- (tert-butyl) sulfamoyl group, N- (cyclobutyl) sulfamoyl group, N- (1-methylbutyl) ) Sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N- (1,1,3,3) -Tetramethylbutyl) sulfamoyl group, N- (2-hydroxybutyl) sulfamoyl group, N- (4-hydroxybutyl) sulfamoyl group, N- (1-hydroxybutan-2-yl) sulfamoyl group, N- (4 4-dimethoxybutyl) sulfamoyl group;
N- (pentyl) sulfamoyl group, N- (isopentyl) sulfamoyl group, N- (neopentyl) sulfamoyl group, N- (tert-pentyl) sulfamoyl group, N- (cyclopentyl) sulfamoyl group, N- (1,4-dimethyl) Pentyl) sulfamoyl group, N- (2,5-dichloropentyl) sulfamoyl group;
N- (hexyl) sulfamoyl group, N- (cyclohexyl) sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (methoxyhexyl) sulfamoyl group, N- (methylcyclohexyl) sulfamoyl group;
N- (heptyl) sulfamoyl group, N- (cycloheptyl) sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group;
N- (octyl) sulfamoyl group, N- (cyclooctyl) sulfamoyl group;
An N- (nonyl) sulfamoyl group;
N- (decyl) sulfamoyl group, N- (tricyclodecyl) sulfamoyl group;
N- (methoxy) sulfamoyl group, N- (tert-butoxy) sulfamoyl group;
An N- (2-norbornyl) sulfamoyl group, an N- (morpholinyl) sulfamoyl group; and a group represented by the following formula:
Etc.

In the above formula, R ³⁹ represents a C _1-3 alkyl group or a C _1-3 alkoxy group, and the hydrogen atom of the alkyl group and alkoxy group may be substituted with a halogen atom. Examples of R ³⁹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a perfluoromethyl group, and the like; and a methoxy group, an ethoxy group, a propoxy group, and the like.

In the above formula, R ⁴⁰ represents a C _1-3 alkyl group, a C _1-3 alkoxy group, a halogen atom or a nitro group, and the hydrogen atom of the alkyl group and alkoxy group may be substituted with a halogen atom. . Examples of the ^optionally substituted alkyl group for R ⁴⁰ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a perfluoromethyl group. Examples of the C _1-3 alkoxy group for R ⁴⁰ include a methoxy group, an ethoxy group, and a propoxy group. Examples of the halogen atom for R ⁴⁰ include a fluorine atom, a chlorine atom, and a bromine atom.

Examples of —SO ₂ NR ⁹ R ¹⁰ in the dye (E1) include groups represented by the following formulas.

R ⁴⁰ in the above formula has the same meaning as described above.

As —SO ₂ NHR ⁹ , —SO ₂ NHR ²⁹ and —SO ₂ NR ⁹ R ¹⁰ , R ⁹ , R ¹⁰ and R ²⁹ are each independently a linear or branched C _1-10 alkyl. Group, C _5-7 cycloalkyl group, linear or branched C _2-10 alkenyl group (eg allyl group), C _6-10 aryl group (eg phenyl group), C _8-10 aralkyl group, hydroxy A group-containing C _2-8 alkyl group, and a hydroxy group-containing C _6-8 aryl group, a C _2-8 alkoxy group-containing C _2-8 alkyl group, or a C _2-8 alkoxy group-containing C _6-8 aryl group. those are preferred; R ^9, R ¹⁰ and R ²⁹ are each independently, more preferably those which are branched C _6-8 alkyl group; R ^9, R ¹⁰ and R ²⁹ is 2-ethylhexyl group Are more preferred {i.e., N- (2-ethylhexyl) sulfanyl group}.

  Among the dyes (E1-1), compounds having a structure represented by the formula (E1-1-1) are preferable.

In the formula (E1-1-1), R ⁴¹ represents a hydrogen atom, —CO ₂ H, —SO ₃ ⁻ , —SO ₃ H, or —SO ₂ NHR ⁴³ . R ⁴² each independently represents a hydrogen atom, —CO ₂ H, —SO ₃ ⁻ , —SO ₃ H, or —SO ₂ NHR ⁴³ . R ⁴³ represents a linear or branched C _1-10 alkyl group, preferably a branched C _3-10 alkyl group, more preferably a branched C _6-8 alkyl group, More preferably, it represents a 2-ethylhexyl group.

Among the dyes (E1-1-1), a compound having a structure represented by the formula (E1-1-1a) is preferable {in the formula (E1-1-1a), R ⁴¹ and R ⁴³ are the same as described above. Meaning. }.

The dye (E1-1-1a) includes a tautomer represented by the formula (E1-1-1b) {in the formula (E1-1-1b), R ⁴¹ has the same meaning as described above. }.

  In the dye (E1-1), a compound having a structure represented by the formula (E1-1-2) or the formula (E1-1-3) is more preferable.

In formula (E1-1-2) and formula (E1-1-3), R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represents —SO ₃ ⁻ , —SO ₃ Na or —SO ₂ NHR ⁴³ . And preferably at least one of R ⁴⁴ , R ⁴⁵ and R ⁴⁶ represents —SO ₂ NHR ⁴³ .
R ⁴³ in formula (E1-1-2) has the same meaning as described above.

  Among the dyes (E1-1), compounds having a structure represented by the formula (E1-1-4) or the formula (E1-1-5) are more preferable.

In formulas (E1-1-4) and (E1-1-5), R ⁴⁷ and R ⁴⁸ each independently represent —SO ₃ ⁻ , —SO ₃ H or —SO ₂ NHR ⁴³ , and p1 and q1 Each independently represents 0 or 1. However, p1 and q1 being 0 means that R ⁴⁷ and R ⁴⁸ do not exist, respectively. R ⁴⁹ represents —SO ₃ ⁻ , —SO ₃ H or —SO ₂ NHR ⁴³ group.
Preferably at least one of R ⁴⁷ , R ⁴⁸ and R ⁴⁹ represents —SO ₂ NHR ⁴³ .
R ⁴³ in formula (E1-1-4) has the same meaning as described above.

Among the dyes (E1-1-4), a compound having a structure represented by the formula (E1-1-4a) is preferable {In the formula (E1-1-4a), Ra represents ^a 2-ethylhexyl group} .

The dye (E1) having a substituted sulfamoyl group can be produced, for example, by sulfonamidation of a dye or dye intermediate having —SO ₃ ^— or —SO ₃ H. Specifically, the dye (E1) having —SO ₂ NHR ⁹ is prepared by first chlorinating a dye having —SO ₃ ^— or —SO ₃ H by a conventional method to produce a dye having —SO ₂ Cl, and the like. It can be produced by reacting this with an amine represented by R ⁹ —NH ₂ . A coloring material having —SO ₃ ^— or —SO ₃ H as a starting material can be produced, for example, by the method described in JP-A-3-78702, page 3, upper right column to lower left column. Moreover, the pigment | dye used as a starting material is marketed. For example, sulforhodamine B, sulforhodamine B, C.I. I. Solvent Red 49, Rhodamine B, C.I. I. Acid Violet 102, C.I. I. Acid Violet 102, C.I. I. Dye (E1-1-1) to Dye (E1-1-5) can be produced by sulfonamidating Acid Red 289 or the like.

  When the dye is used, the content thereof is preferably 3% by mass or more and 80% by mass or less (more preferably 70% by mass or less, and further preferably 50% by mass or less) in the colorant (E). When using a dye, the remaining colorant (E) is preferably a pigment (more preferably an organic pigment). When the colorant (E) comprising a dye and a pigment within the above range is used, the transmission spectrum can be easily optimized, and a coating film and pattern having high contrast and lightness, and good heat resistance and chemical resistance can be obtained. can get. The pigment used in combination with the dye is preferably a blue pigment, more preferably C.I. I. Pigment Blue 15: 6. The mass ratio of “dye”: “CI pigment blue 15: 6” is preferably 3:97 to 50:50.

  The colorant (E) may further contain a pigment in addition to the dye. A pigment may be used individually by 1 type and may use 2 or more types together.

Specific examples of the pigment include compounds classified as pigments according to a color index (published by The Society of Dyers and Colorists). Specifically, for example,
C. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as pigment ranges 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. Black pigments such as CI Pigment Black 1 and 7;
Etc.

  Examples of yellow pigments include C.I. I. Pigment Yellow 138, 139 and 150 are preferable. Examples of red pigments include C.I. I. Pigment Red 177, 209, 242 and 254 are preferable. Examples of the violet color pigment include C.I. I. Pigment Violet 23 is preferable. Examples of green pigments include C.I. I. Pigment Green 7, 36, and 58 are preferable. When the composition of the present invention comprises a dye (E1), the composition of the present invention is preferably a blue pigment, more preferably C.I. I. Pigment blue 15: 3 and C.I. I. Pigment Blue 15: 6, at least one selected from the group consisting of C.I. I. Pigment Blue 15: 6.

  If necessary, the pigment is rosin-treated; surface treatment using a pigment derivative or pigment dispersant into which an acidic group or basic group has been introduced; graft treatment to the pigment surface with a polymer compound; sulfuric acid atomization method Or the like; cleaning treatment with an organic solvent or water for removing impurities; removal treatment of ionic impurities by an ion exchange method or the like;

  When the colorant (E) contains a dye and a pigment, the content of the pigment is preferably 2% by mass or more (more preferably 5% by mass or more, further) in the colorant (E) (that is, the total of the dye and the pigment). Preferably it is 10 mass% or more), preferably 98 mass% or less (more preferably 95 mass% or less).

  Pigments with a uniform particle size are preferred. Moreover, when using a pigment, it is preferable to disperse | distribute a pigment uniformly in a solution using a pigment dispersant. A pigment dispersant may be used individually by 1 type, and may use 2 or more types together. When a pigment dispersant is used, the amount used is preferably 0.05 parts by mass or more and 1 part by mass or less (more preferably 0.5 parts by mass or less) per 1 part by mass of the pigment. If the pigment dispersant is used in an amount within this range, a uniformly dispersed pigment dispersion tends to be obtained.

  A surfactant can be used as the pigment dispersant. Surfactants can be electrically classified into cationic, anionic, nonionic, and amphoteric, and compounds can be classified into ester, amine, acrylic, silicone, fluorine, and the like. These surfactants may be appropriately selected and used depending on the pigment and the like. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. It is done. Commercially available surfactants such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (Mitsubishi Materials Electronics Chemicals Co., Ltd.), MegaFac (DIC ( Co., Ltd.), FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard (manufactured by Asahi Glass Co., Ltd.), Surflon (manufactured by AGC Seimi Chemical Co., Ltd.), Solsperse (manufactured by Geneca Corporation), EFKA (manufactured by CIBA) ), Azisper (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by Big Chemie), etc.

<Other additives (F)>
The composition of this invention may contain the other additive (F) as needed. Examples of other additives (F) include surfactants and the above-described pigment dispersants. The surfactant is preferably a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. One surfactant may be used alone, or two or more surfactants may be used.

  Examples of the silicone surfactant include a surfactant having a siloxane bond. Silicone surfactants are Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (Toray Silicone Co., Ltd.), KP321, KP322, KP323, Product names such as KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (made by Momentive Performance Materials Japan GK) It is commercially available.

  Examples of the fluorosurfactant include a surfactant having a fluorocarbon chain. Fluorosurfactants are Florard FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F177, F183, R30 (DIC Corporation) ), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) ), E5844 (manufactured by Daikin Fine Chemical Laboratory), BM-1000, BM-1100 (manufactured by BM Chemie), and the like.

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Silicone-based surfactants having a fluorine atom are commercially available under trade names such as Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

  When using surfactant, the content becomes like this. Preferably it is 0.00001-0.1 mass% with respect to a composition, More preferably, it is 0.00005-0.01 mass%. If content of surfactant is in the said range, there exists a tendency for the flatness of a coating film and a pattern to become favorable.

<Solvent (G)>
Examples of the solvent (G) include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, N-methylpyrrolidone, dimethyl sulfoxide and the like.

  Examples of ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol. Monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene Glycol monopropyl ether acetate, propylene glycol monomethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, anisole, phenetole, and the like methyl anisole.

  Examples of aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.

  Examples of ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, cyclopentanone, and cyclohexanone. Etc.

  Examples of alcohols include methanol, ethanol, propanol, butanol, 3-methoxy-1-butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

  Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate , Methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2 -Methyl oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methyl Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 3-methoxy Examples include butyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.

  Examples of amides include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

  Among these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-1-butanol, and 3-methoxybutyl acetate are preferable, and these mixed solvents Is more preferable.

  The content of the solvent (G) is preferably 70% by mass or more (more preferably 75% by mass or more), preferably 95% by mass or less (more preferably 90% by mass or less) with respect to the composition. If content of a solvent (G) is in the said range, the flatness at the time of apply | coating a composition will become favorable. In addition, when forming the color filter, insufficient color density can be prevented, and the display characteristics of the color filter tend to be good.

<Pattern and paint film>
A pattern is preferably formed from the composition of the present invention by a photolithographic method. If the composition of the present invention is used, a development residue in the photolithographic method can be effectively prevented. In the photolithographic method, a pattern is usually formed through steps of application of a photosensitive composition, solvent removal, heating before exposure (pre-baking), exposure, development, and heating after development (post-baking).

  A pattern can be formed from the composition of the present invention by a method other than the photolithography method. For example, the pattern can also be formed by applying the composition of the present invention in a pattern using, for example, an inkjet device and then photopolymerizing. Moreover, after apply | coating the composition of this invention to a base | substrate (for example, the board | substrate with which the resin layer was formed, etc.) by well-known methods, such as a spin coat method, a coating film can also be formed by photopolymerizing.

  The coating film and pattern of this invention are suitable for the coloring pattern of the color filter of a display apparatus, for example. In particular, a color filter containing at least one selected from the group consisting of the coating film and pattern of the present invention is preferable.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples, and appropriate modifications are made within a range that can meet the above and the following purposes. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.
In the following, “%” and “parts” in the component amounts are “% by mass” and “parts by mass” unless otherwise specified.

1. Synthesis of Resin (A) (1) Synthesis of Resin (A1) Nitrogen was flowed at a rate of 0.02 L / min into a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and gas inlet tube to form a nitrogen atmosphere. 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added and heated to 70 ° C. with stirring. Then 60 parts of methacrylic acid; and 4,5-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate {ie monomer (b1-1-1)} and 3,4- Epoxy tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate {ie monomer (b1-2-1)} mixture {monomer in mixture (b1-1-1) : Monomer (b1-2-1) molar ratio = 50:50} 240 parts; was dissolved in 140 parts of 3-methoxybutyl acetate to prepare a monomer solution. The monomer solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel. On the other hand, a polymerization initiator solution in which 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts of 3-methoxybutyl acetate was added for 4 hours using another dropping funnel. And dropped into the flask. After completion of the dropwise addition of the polymerization initiator solution, the mixture was held at 70 ° C. for 4 hours, and then cooled to room temperature, and the weight average molecular weight Mw: 1.3 × 10 ⁴ , molecular weight distribution: 2.5, solid content 33% A resin (A1) solution having an acid value of 34 mg-KOH / g was obtained.

(2) Synthesis of resin (A2) Propylene glycol monomethyl ether acetate was made to flow into a nitrogen atmosphere by flowing nitrogen at 0.02 L / min into a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and gas introduction tube. 333 parts were added and heated to 100 ° C. with stirring. Next, 22.0 parts of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate (common name: dicyclopentanyl methacrylate, manufactured by Hitachi Chemical Co., Ltd .: “FA-513M”), benzyl methacrylate A solution was prepared by dissolving 70.5 parts, 43.0 parts of methacrylic acid, and 3.6 parts of azobisisobutyronitrile in 164 parts of propylene glycol monomethyl ether acetate. The said solution was dripped in the flask kept at 100 degreeC over 2 hours using the dropping funnel. After completion of the dropwise addition, stirring was further continued at 100 ° C. for 5 hours. After completion of the stirring, air was introduced into the flask through a gas introduction tube, and the atmosphere in the flask was changed to air, and then 35.5 parts of glycidyl methacrylate, 0.9 part of trisdimethylaminomethylphenol and 0.145 part of hydroquinone were placed in the flask. The mixture was kept at 110 ° C. for 6 hours, and then cooled to room temperature. A resin (weight average molecular weight Mw: 9.0 × 10 ³ , solid content: 38.5%, acid value: 31 mg-KOH / g) A2) A solution was obtained.

The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the resin are values determined by gel permeation chromatography under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Test liquid solid concentration: 0.001 to 0.01%
Injection volume: 50 μL
Detector: RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

2. Synthesis of dye In a flask equipped with a condenser and a stirrer, a mixture of a compound represented by the formula (E0-1) and a compound represented by the formula (E0-2) (Chugai Amino Fast Pink R; manufactured by Chugai Kasei) 15 Part, 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide were added dropwise and 10.9 parts of thionyl chloride was added dropwise while maintaining at 20 ° C. or lower with stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixture of 375 parts of ion exchange water with stirring to precipitate crystals. The precipitated crystals are separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C., and dye (E1-1-4a) to dye (E1-1-4f) and dye (E1-1-5a). And 11.3 parts of a mixture of dye (E1-1-5b) were obtained {Formula (E1-1-4a) to Formula (E1-1-4f), Formula (E1-1-5a) and Formula (E1- In 1-5b), R ^a represents a 2-ethylhexyl group. }. Hereinafter, this dye mixture is abbreviated as “dye (E10)”.

3. Preparation of Composition Components shown in Tables 1 and 2 were mixed to prepare Compositions 1 to 7 and Comparative Composition H1. The pigments marked with “*” in Table 1, acrylic pigment dispersants, and propylene glycol monomethyl ether acetate are mixed with each other and prepared with a bead mill to prepare a pigment dispersion. Mixed with the ingredients.

The water solubility of the polymerizable compound (B) used in the examples was measured as follows: After adding water to 100 parts of the polymerizable compound (B) in the screw tube, the mix rotor (VMR-5; ASONE) The product was stirred at room temperature for 1 hour. The screw tube was then sealed and allowed to stand in an oven at 40 ° C. for 24 hours. By visually observing after this standing, when the content of the screw tube was transparent and uniform, it was determined that the content was dissolved. On the other hand, when the contents were opaque, a part was deposited, or the liquid layer was separated, it was determined that the contents were not dissolved. The amount of water was changed stepwise by the procedure as described above, and the maximum amount of dissolved water was defined as the solubility of the polymerizable compound (B) in water.
Table 2 shows the water solubility of the polymerizable compound (B1) used in Compositions 1-7. In addition, the solubility of water of dipentaerythritol hexaacrylate which is a polymeric compound (B2) was 1 part or less.

4). Evaluation The residue during pattern development, the chromaticity (By and lightness) of the obtained pattern, and the color difference ΔEab * before and after the pattern was heated at 230 ° C. for 2 hours were evaluated as follows.

(1) Pattern development The composition was applied on a 2-inch square glass substrate (Eagle 2000; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C for 3 minutes. After cooling, the distance between the substrate coated with this composition and the quartz glass photomask having a pattern is set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Corp.) is used, and 150 mJ / cm in an air atmosphere. The exposure was performed with an exposure amount of ² (based on 365 nm). The coated film after the exposure was developed by immersing in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 80 seconds. After washing this with water, it was post-baked in an oven at 220 ° C. for 20 minutes. When the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) after standing to cool, the film thickness of the obtained pattern was 2.0 μm.

(2) Residue evaluation The unexposed part of the obtained pattern is visually observed, and if the color derived from the colorant (E) is not recognized, the residue is good (◯), and if the color is recognized, it is poor (× ). The results are shown in Table 3.

(3) Evaluation of chromaticity (By and lightness) of pattern About the pattern on the obtained glass substrate, spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and C light source The xy chromaticity coordinates (Bx, By) and brightness in the CIE XYZ color system were measured using a color matching function. The results of By and brightness are shown in Table 3.

(4) Color difference ΔEab * evaluation of the pattern before and after heating Before and after heating the pattern on the obtained glass substrate in an oven at 230 ° C. for 2 hours, xy chromaticity coordinates (Bx, By) and brightness were measured. The color difference ΔEab * before and after heating was calculated. The results are shown in Table 3.

  As shown in Tables 1 to 3, Composition 1 containing a polymerizable compound (B1) having a water solubility of 25 to 100 parts by mass in a polymerizable compound (B) at 4.8 to 20% by mass. In -7, no residue was observed in the unexposed part, whereas in composition H1 not containing the polymerizable compound (B1), a residue was observed. Further, the color difference ΔEab * before and after heating of the patterns obtained from the compositions 1 to 7 is 5 or less (specifically 3 or 4), and it can be determined that these patterns have good heat resistance.

  The composition of the present invention can effectively prevent development residue in the photolithographic method. Moreover, the coating film and pattern obtained from the composition of this invention show favorable heat resistance. Such a coating film and pattern are useful for manufacturing the component of a display apparatus, especially a color filter.

Claims (12)

A colored photosensitive resin composition comprising a resin (A), a polymerizable compound (B), a photopolymerization initiator (C), a colorant (E), and a solvent (G);
The polymerizable compound (B) contains the polymerizable compound (B1),
Content of the said polymeric compound (B1) is 0.5-20 mass% in polymeric compound (B),
When water is added to the polymerizable compound (B1) at 40 ° C., the amount of water to be dissolved is 25 to 100 parts by mass with respect to 100 parts by mass of the polymerizable compound (B1). A colored photosensitive resin composition. The polymerizable compound (B) contains the polymerizable compound (B1) and the polymerizable compound (B2),
The total content of the polymerizable compound (B1) and the polymerizable compound (B2) is 95% by mass or more in the polymerizable compound (B),
The amount of water dissolved when adding water to the polymerizable compound (B2) at 40 ° C is less than 25 parts by mass with respect to 100 parts by mass of the polymerizable compound (B2). Colored photosensitive resin composition.   The colored photosensitive resin composition according to claim 1 or 2, wherein the colorant (E) contains a dye.   A structural unit in which the resin (A) is derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride; a carbon-carbon double bond and a cyclic ether structure A colored photosensitive resin composition according to any one of claims 1 to 3, which is a copolymer comprising: The monomer (b) having a carbon-carbon double bond and a cyclic ether structure is at least selected from the group consisting of a compound represented by the formula (b1-1) and a compound represented by the formula (b1-2). The colored photosensitive resin composition according to claim 4, which is one type.
[In Formula (b1-1) and Formula (b1-2), R ¹ represents a hydrogen atom or a C _1-4 saturated aliphatic hydrocarbon group, and the hydrogen atom of the saturated aliphatic hydrocarbon group is —OH. May be substituted.
L ¹ represents a single bond or a divalent C _1-6 saturated aliphatic hydrocarbon group, and —CH ₂ — of the divalent saturated aliphatic hydrocarbon group represents —O—, —S— or —NR. ² - may be substituted with, said R ² represents a hydrogen atom or a C _1-10 saturated aliphatic hydrocarbon group.
R ¹ and L ¹ in formula (b1-1) may be the same as or different from R ¹ and L ^{1 in} formula (b1-2), respectively. ] The colored photosensitive resin composition according to claim 3, wherein the dye is a compound having a structure represented by the formula (E1).
[In the formula (E1), R ^{3 to} R ⁶ each independently represents a hydrogen atom, —R ⁸ or a C _6-10 aromatic hydrocarbon group, and the hydrogen atom contained in the aromatic hydrocarbon group is A halogen atom, —R ⁸ , —OH, —OR ⁸ , —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ H, —SO ₃ ⁻ , —SO ₃ M ¹ , —SO ₃ R ⁸ , or —SO ₂ Optionally substituted with NR ⁹ R ¹⁰ . m1 represents 0 or 1. However, m1 being 0 means that there is no positive charge on R ⁵ and the nitrogen atom.
In the formula (E1), R ⁷ represents —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ H, —SO ₃ ⁻ , —SO ₃ M ¹ , —SO ₃ R ⁸ , or —SO ₂ NR ⁹ R. Represents ¹⁰ . n1 represents the integer of 0-5. However, n1 being 0 means that R ⁷ does not exist, and when n 1 is 2 or more, a plurality of R ⁷ may be the same or different.
R ⁸ represents a C _1-10 saturated aliphatic hydrocarbon group, and the hydrogen atom of the saturated aliphatic hydrocarbon group may be substituted with —OR ¹¹ or a halogen atom, The hydrocarbon group —CH ₂ — may be substituted with —O—, —CO—, or —NR ¹¹ —.
R ⁹ and R ¹⁰ each independently represents a hydrogen atom, a linear or branched C _1-10 saturated aliphatic hydrocarbon group, a C _3-30 alicyclic hydrocarbon group, or —Ar ¹ . And the hydrogen atom of the saturated aliphatic hydrocarbon group and alicyclic hydrocarbon group may be substituted with —OH, a halogen atom, —Ar ¹ , —CH═CH ₂ or —CH═CHR ^8. In the above saturated aliphatic hydrocarbon group and alicyclic hydrocarbon group, —CH ₂ — may be substituted with —O—, —S—, —CO—, —NH— or —NR ⁸ —. , R ⁹ and R ¹⁰ may combine with each other to form a 3- to 10-membered ring, and the hydrogen atom of the ring may be substituted with —R ⁸ , —OH or —Ar ¹ . R ⁸ has the same meaning as described above.
R ¹¹ represents a hydrogen atom or a C _1-10 saturated aliphatic hydrocarbon group, and the hydrogen atom of the saturated aliphatic hydrocarbon group may be substituted with a halogen atom, and the saturated aliphatic carbon group The —CH ₂ — of the hydrogen group may be substituted with —O— or —CO—.
Ar ¹ represents a C _6-10 aromatic hydrocarbon group or a 5- to 7-membered aromatic heterocyclic group, and the hydrogen atoms of the aromatic hydrocarbon group and aromatic heterocyclic group are: —OH, —R ⁸ , —OR ⁸ , —NO ₂ , —CH═CH ₂ , —CH═CHR ⁸ or a halogen atom may be substituted. R ⁸ has the same meaning as described above.
M ¹ represents a sodium atom or a potassium atom. ]   The colored photosensitive resin composition according to claim 3 or 6, wherein the colorant (E) further contains a pigment.   The pigment is C.I. I. The colored photosensitive resin composition according to claim 7, comprising Pigment Blue 15: 6.   The coating film formed using the colored photosensitive resin composition in any one of Claims 1-8.   The pattern formed using the colored photosensitive resin composition in any one of Claims 1-8.   The pattern according to claim 10 formed by a photolithographic method.   A color filter comprising at least one selected from the group consisting of the coating film according to claim 9 and the pattern according to claim 10 and claim 11.