JP2016141770A - Colorant dispersion, photosensitive resin composition comprising the same, and dispersion assistant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colorant dispersion that has good dispersion stability of a colorant even when a content of a dispersant is decreased and that can give a photosensitive resin composition capable of forming a minute pattern having high adhesiveness even with a low dose of exposure light, a photosensitive resin composition comprising the colorant dispersion, and a dispersion assistant.SOLUTION: The colorant dispersion of the present invention comprises a colorant, a dispersant, an oxime compound represented by formula (1), and a solvent. In the formula, Rrepresents a hydrogen atom, a nitro group or a monovalent organic group; Rand Reach represent a linear alkyl group, a cyclic hydrocarbon group or a heteroaryl group, and Rand Rmay be bonded to each other to form a spiro ring; Rrepresents a monovalent organic group; Rrepresents a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent; and m represents 0 or 1. The photosensitive resin composition of the present invention comprises a base resin, a photopolymerization initiator, and the above colorant dispersion. The dispersion assistant of the present invention comprises the above oxime compound.SELECTED DRAWING: None

Description

  The present invention relates to a colorant dispersion, a photosensitive resin composition containing the same, and a dispersion aid.

  The liquid crystal panel includes a black matrix for enhancing the contrast of an image, and a color filter in which an RGB colored layer generally composed of red (R), green (G), and blue (B) colors is formed. . These black matrixes and color filters are coated with a photosensitive resin composition in which black or each colorant is dispersed on a substrate and dried, and then the resulting coating film is exposed and developed to form a desired pattern. It is formed by repeating. In order to produce such a photosensitive resin composition, a colorant dispersion in which a colorant is dispersed is used. For example, Patent Document 1 discloses a pigment dispersion containing a pigment, a solvent, a dispersant, and a specific additive having an azo group, an amide group, and a carbonyl group.

JP 2012-087233 A

  In recent years, technological innovation has progressed in increasing the resolution of liquid crystal panels, and there has been a demand for improved color development of RGB colored layers. The color developability can be improved by increasing the concentration of the colorant in the photosensitive resin composition that gives the RGB colored layer. However, increasing the concentration of the colorant results in a decrease in the sensitivity of the photosensitive resin composition to light. For example, it becomes difficult to form a pattern with a good shape at a low exposure amount, and productivity in the exposure process is increased. Is prone to decline.

  If the amount of the dispersant in the colorant dispersion can be reduced, the amount of the photopolymerization initiator and the amount of light in the photosensitive resin composition obtained from the colorant dispersion are reduced by the amount of the dispersant. The amount of a photopolymerizable compound such as a polymerizable monomer can be increased, and the sensitivity of the photosensitive resin composition to light can be increased. For this purpose, it is required that the colorant has good dispersion stability even if the content of the dispersant is reduced.

  The present invention has been made in view of such conventional circumstances, and even when the content of the dispersant is reduced, the dispersion stability of the colorant is good, and a fine pattern with high adhesion can be obtained even at a low exposure amount. An object is to provide a colorant dispersion capable of providing a formable photosensitive resin composition, a photosensitive resin composition containing the same, and a dispersion aid.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by adding a specific oxime compound to the colorant dispersion, and have completed the present invention. Specifically, the present invention provides the following.

  A first aspect of the present invention is a colorant dispersion containing a colorant, a dispersant, an oxime compound represented by the following formula (1), and a solvent.

（Ｒ^１は水素原子、ニトロ基又は１価の有機基であり、Ｒ^２及びＲ^３は、それぞれ、鎖状アルキル基、環状炭化水素基、又はヘテロアリール基であり、Ｒ^２とＲ^３とは相互に結合してスピロ環を形成してもよく、Ｒ^４は１価の有機基であり、Ｒ^５は、水素原子、置換基を有してもよい炭素原子数１〜１１のアルキル基、又は置換基を有してもよいアリール基であり、ｍは０又は１である。）

(R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, R ² and R ³ are each a chain alkyl group, a cyclic hydrocarbon group, or a heteroaryl group, and R ² and R ³ are ^May combine with each other to form a spiro ring, R ⁴ is a monovalent organic group, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 11 carbon atoms that may have a substituent. Or an aryl group which may have a substituent, and m is 0 or 1.)

  The second aspect of the present invention is a photosensitive resin composition comprising a base resin, a photopolymerization initiator, and the colorant dispersion.

  The third aspect of the present invention is a dispersion aid comprising the oxime compound represented by the above formula (1).

  According to the present invention, it is possible to provide a photosensitive resin composition that has good dispersion stability of the colorant even when the content of the dispersant is reduced, and can form a highly adhesive micropattern even at a low exposure amount. A colorant dispersion, a photosensitive resin composition containing the same, and a dispersion aid can be provided.

<Colorant dispersion>
The colorant dispersion according to the present invention contains a colorant, a dispersant, an oxime compound represented by the above formula (1), and a solvent. The colorant dispersion according to the present invention does not contain a photopolymerizable compound such as a photopolymerizable monomer or a photopolymerization initiator.

[Colorant]
The colorant dispersion according to the present invention contains a colorant. By containing such a colorant, the colorant dispersion according to the present invention is preferably used, for example, for forming a color filter, a paint, a solder resist, an ink jet ink and the like for a liquid crystal display. In addition, the colorant dispersion according to the present invention preferably contains a light-shielding agent as a colorant, and thus is preferably used, for example, as a black matrix forming application in a color filter of a display device. The colorants can be used alone or in combination of two or more.

  Although it does not specifically limit as a coloring agent contained in the coloring agent dispersion liquid which concerns on this invention, A pigment or dye can be used, for example, a color index (CI; The Society of Dyer's and Colorists issue) ), A compound classified as a pigment, specifically, a compound having a color index (CI) number as shown below is preferably used.

  Examples of yellow pigments that can be suitably used include C.I. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same, and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180 , And 185.

  Examples of orange pigments that can be suitably used include C.I. I. Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 2, 5, 13, 14, 16, 17, 19, 20, 21, 22, 23, 24 , 34, 36, 38, 39, 40, 43, 46, 48, 49, 51, 55, 59, 61, 62, 63, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74 , 75, 77, 78, and 79.

  Examples of purple pigments that can be suitably used include C.I. I. Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same, and only the number is described), 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5 : 1, 14, 15, 16, 19, 23, 25, 27, 29, 30, 32, 36, 37, 38, 39, 40, 42, 44, 47, 49, and 50, and C.I. I. Solvent Violet 13, C.I. I. Solvent violet 36 may be mentioned.

  Examples of red pigments that can be suitably used include C.I. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same, and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57: 1, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 1 8, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265, 270, and 272.

  Examples of blue pigments that can be suitably used include C.I. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same, and only numbers are described), 2, 15 (including 15: 1 to 15: 6, etc., in particular, 15: 3, 15: 4, 15: 6), 16, 22, 60, 64, 66, and 75.

  Examples of pigments of other hues that can be suitably used include C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37, C.I. I. Pigment Green 58 and other green pigments, C.I. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigments such as CI Pigment Brown 28, C.I. I. And black pigments such as CI Pigment Black 1 (hereinafter, “CI Pigment Black” is the same and only the numbers are described), 7, 30, 31, 32, 33, 34, and the like.

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

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

  Resin-coated carbon black has lower electrical conductivity than carbon black without resin coating, so there is little leakage of current when used as a black matrix for liquid crystal display elements such as liquid crystal display, and high reliability and low A display with power consumption can be manufactured.

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

  Inorganic pigments and organic pigments may be used alone or in combination of two or more, but when used in combination, the organic pigment is in the range of 10 to 80 parts by mass relative to 100 parts by mass of the total amount of inorganic pigment and organic pigment. It is preferable to use in the range of 20 to 40 parts by mass.

  The colorant contained in the colorant dispersion according to the present invention may be a pigment made of a nitrogen-containing aromatic ring compound. The pigment comprising a nitrogen-containing aromatic ring compound is not particularly limited. For example, diketopyrrolopyrrole pigment, phthalocyanine pigment, perylene pigment, azo pigment, quinacridone pigment, benzimidazolone pigment, isoindolinone Pigments, dioxazine pigments, indanthrene pigments and the like, and diketopyrrolopyrrole pigments, phthalocyanine pigments, and / or perylene pigments are preferably used.

  It does not specifically limit as a diketopyrrolopyrrole pigment, For example, the compound represented by a following formula (b-1) is mentioned.

In formula (b-1), A ³ and A ⁴ are each independently a halogen atom, methyl group, ethyl group, tert-butyl group, phenyl group, N, N-dimethylamino group, trifluoromethyl group, cyano And k and k ′ each independently represent an integer of 0 to 5, and when k and k ′ are each an integer of 2 or more, a plurality of A ³ and A ⁴ are the same or different. May be. )

  In formula (b-1), k and k ′ are each independently an integer of 0 to 5. Among these, k and k ′ are each preferably an integer of 0 to 3 and k and k ′ are each independently 0 from the viewpoint of achieving high contrast and easy adjustment of red color suitable for a color filter or the like. Or it is more preferable that it is an integer of 1.

  Among the diketopyrrolopyrrole pigments, C.I. C. is particularly preferable because a color filter having high brightness and high contrast can be formed. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 270, C.I. I. Pigment red 272, C.I. I. Pigment orange 71, C.I. I. Pigment Orange 73 is preferable, and C.I. I. Pigment red 254, C.I. I. More preferably, it is CI Pigment Red 255. The diketopyrrolopyrrole pigments can be used singly or in combination of two or more.

  The average primary particle size of the diketopyrrolopyrrole pigment used in the present invention is not particularly limited as long as it can produce a desired color. From the viewpoint of improving the contrast, it is preferably in the range of 10 to 50 nm, and more preferably in the range of 10 to 30 nm. When the average primary particle diameter of the pigment is within the above range, for example, the color filter can be made to have high contrast and high quality. In addition, the average particle diameter of the pigment can be obtained by a method of directly measuring the size of primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle are measured, and the average is taken as the particle diameter of the particle. Next, for 100 or more particles, the volume (mass) of each particle is obtained by approximating a cuboid with the obtained particle size, and the volume average particle size is obtained and used as the average particle size. The same result can be obtained by using either a transmission type (TEM) or a scanning type (SEM) as an electron microscope.

  The diketopyrrolopyrrole pigment used in the present invention can be produced by a known method such as a recrystallization method or a solvent salt milling method. Commercially available diketopyrrolopyrrole pigments may also be used.

  It does not specifically limit as a phthalocyanine pigment, For example, the compound represented by a following formula (b-2) is mentioned.

[Wherein, X _{1 to} X ₄ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. A heterocyclic group that may have a substituent, an alkoxyl group that may have a substituent, an aryloxy group that may have a substituent, an alkylthio group that may have a substituent, or a substituent. Represents an optionally substituted arylthio group. Y _{1 to} Y ₄ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group. M represents a metal atom such as a copper atom or a zinc atom. m1, m2, m3, m4, n1, n2, n3, and n4 each independently represents an integer of 0 to 4, and m1 + n1, m2 + n2, m3 + n3, m4 + n4 are each an integer of 0 to 4, and are the same But it may be different. ]

In General Formula (b-2), X _{1 to} X ₄ may be the same or different, and specific examples thereof include an alkyl group that may have a substituent and an aryl group that may have a substituent. A cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, substituted Examples thereof include an alkylthio group which may have a group and an arylthio group which may have a substituent. When X _{1 to} X ₄ have a substituent, the substituents may be the same or different. Specific examples thereof include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, an amino group, a hydroxyl group and a nitro group. In addition to the characteristic groups such as alkyl group, aryl group, cycloalkyl group, alkoxyl group, aryloxy group, alkylthio group, and arylthio group. Moreover, there may be a plurality of these substituents.

  As the “alkyl group” of the alkyl group which may have a substituent, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, Examples include a linear or branched alkyl group such as an n-octyl group, a stearyl group, and a 2-ethylhexyl group. Examples of the “alkyl group having a substituent” include a trichloromethyl group, a trifluoromethyl group, 2,2, 2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4 -Methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group, etc. .

  Examples of the “aryl group” of the aryl group which may have a substituent include a phenyl group, a naphthyl group, and an anthryl group, and the “aryl group having a substituent” includes a p-methylphenyl group, p- Bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl Group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group and the like.

  Examples of the “cycloalkyl group” of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like, and examples of the “cycloalkyl group having a substituent” include 2,5 -A dimethylcyclopentyl group, 4-tert- butyl cyclohexyl group, etc. are mentioned.

  Examples of the “heterocyclic group” of the heterocyclic group which may have a substituent include a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, an acridinyl group, and the like. Examples of the “cyclic group” include a 3-methylpyridyl group, an N-methylpiperidyl group, and an N-methylpyrrolyl group.

  As the “alkoxyl group” of the alkoxyl group which may have a substituent, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2 , 3-dimethyl-3-pentyloxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group and the like linear and branched alkoxyl groups such as “alkoxyl having a substituent” Examples of the group include trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2-ditrifluoromethylpropoxy group, 2- Ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group, etc. And the like.

  Examples of the “aryloxy group” of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, an anthryloxy group, and the like, and the “aryloxy group having a substituent” includes p-methyl. Examples include phenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group.

  Examples of the “alkylthio group” of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, and an octadecylthio group. Examples of the “alkylthio group having a substituent” include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group, and the like.

  Examples of the “arylthio group” of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and the like, and “an arylthio group having a substituent” Chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group, nitrophenylthio group, 2-aminophenylthio group, 2-hydroxyphenylthio group and the like.

Next, specific examples of Y _{1 to} Y ₄ include a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —), a sulfamoyl group ( H ₂ NSO ₂ —). A phthalimidomethyl group having a substituent represents a structure in which a hydrogen atom in the phthalimidomethyl group is substituted by a substituent, and a sulfamoyl group having a substituent is a hydrogen atom in the sulfamoyl group substituted by a substituent. Represents the resulting structure. Preferred Y _{1 to} Y ₄ are a halogen atom and a sulfamoyl group. m1~m4 is 0 _(i.e., no Y 1 to Y ₄₎ phthalocyanine compound can be preferably used. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The “substituent” of the phthalimidomethyl group which may have a substituent and the sulfamoyl group which may have a substituent has the same meaning as the substituents of X _{1 to} X ₄ .

  Examples of the phthalocyanine pigment include C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37, C.I. I. Pigment green 58, C.I. I. Pigment blue 16, C.I. I. Pigment blue 75, and C.I. I. Pigment Blue 15 (including 15: 1 to 15: 6) and the like are preferable. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment Blue 15: 1 to 15: 6 is more preferable. A phthalocyanine pigment can be used individually by 1 type or in combination of 2 or more types.

  The phthalocyanine pigment used in the present invention can be produced by a known method. Commercially available phthalocyanine pigments may also be used.

  As a perylene pigment, a perylene pigment represented by the following formula (e-1), a perylene pigment represented by the following formula (e-2), and a perylene pigment represented by the following formula (e-3) Pigments. Commercially available products include product names K0084 and K0086 manufactured by BASF, C.I. I. Pigment Black 21 (hereinafter, “CI Pigment Black” is the same and only the numbers are described), 30, 31, 32, 33, 34, and the like can be preferably used as the perylene pigment.

式（ｅ−１）中、Ｒ^ｅ１及びＲ^ｅ２は、それぞれ独立に炭素原子数１〜３のアルキレン基を表し、Ｒ^ｅ３及びＲ^ｅ４は、それぞれ独立に、水素原子、水酸基、メトキシ基、又はアセチル基を表す。

In formula (e-1), R ^e1 and R ^e2 each independently represent an alkylene group having 1 to 3 carbon atoms, and R ^e3 and R ^e4 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or Represents an acetyl group.

式（ｅ−２）中、Ｒ^ｅ５及びＲ^ｅ６は、それぞれ独立に、炭素原子数１〜７のアルキレン基を表す。

In formula (e-2), R ^e5 and R ^e6 each independently represent an alkylene group having 1 to 7 carbon atoms.

式（ｅ−３）中、Ｒ^ｅ７及びＲ^ｅ８は、それぞれ独立に、水素原子、炭素原子数１〜２２のアルキル基であり、Ｎ，Ｏ、Ｓ、又はＰのヘテロ原子を含んでいてもよい。Ｒ^ｅ７及びＲ^ｅ８がアルキル基である場合、当該アルキル基は、直鎖状であっても、分岐鎖状であってもよい。

In formula (e-3), R ^e7 and R ^e8 are each independently a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, and may contain a heteroatom of N, O, S, or P. Good. When R ^e7 and R ^e8 are alkyl groups, the alkyl group may be linear or branched.

  Examples of the compound represented by the above formula (e-1), the compound represented by the formula (e-2), and the compound represented by the formula (e-3) include, for example, JP-A-62-17353. Can be synthesized using the method described in JP-B 63-26784. That is, perylene-3,5,9,10-tetracarboxylic acid or a dianhydride thereof and an amine are used as raw materials, and a heating reaction is performed in water or an organic solvent. The target product can be obtained by reprecipitation of the obtained crude product in sulfuric acid or recrystallization in water, an organic solvent or a mixed solvent thereof.

  In order to disperse the perylene pigment satisfactorily, the average particle size of the perylene pigment is preferably 10 to 1000 nm.

  The content of the colorant is preferably 5 to 95% by mass and more preferably 25 to 90% by mass with respect to the solid content of the colorant dispersion according to the present invention.

[Dispersant]
The colorant dispersion according to the present invention contains a dispersant. When the colorant dispersion contains a dispersant, the colorant is easily dispersed uniformly in the colorant dispersion. A dispersing agent may be used independently and may use 2 or more types together.

  Examples of the dispersant include known ones, and it is preferable to use a polyethyleneimine polymer dispersant, a urethane resin polymer dispersant, and an acrylic resin polymer dispersant.

  In the colorant dispersion according to the present invention, the content of the dispersant is preferably 1 to 50 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the colorant. More preferably, it is -15 mass parts. When the content of the dispersant is in the above range, the uniform dispersion of the colorant in the colorant dispersion according to the present invention is further facilitated. In addition, as the upper limit is smaller, in the photosensitive resin composition described later, the balance of each component tends to be better, and the blending amount of other components in the photosensitive resin composition can be relatively increased. It becomes easy to improve other characteristics. As for the sensitivity characteristics, the effect is particularly good when a blue pigment that absorbs the photosensitive wavelength is used.

[Oxime compounds]
The colorant dispersion according to the present invention contains an oxime compound represented by the following formula (1). This oxime compound has both a function as a photopolymerization initiator and a function as a dispersion aid. Therefore, when the colorant dispersion containing the colorant contains the oxime compound, the dispersion stability of the colorant tends to be good even if the content of the dispersant is reduced. That is, by using the oxime compound, it becomes easy to reduce the content of the dispersant in the colorant dispersion without impairing the dispersion stability of the colorant. As a result, a part of the dispersant is replaced with the oxime compound. Since the oxime compound also functions as a photopolymerization initiator, the above replacement corresponds to reducing the content of the dispersant and increasing the content of the photopolymerization initiator. Therefore, in the photosensitive resin composition obtained from the colorant dispersion containing the oxime compound, the content of the photopolymerization initiator can be increased. From the photosensitive resin composition, a low exposure amount and high adhesion can be obtained. It becomes easy to form a minute pattern. The said oxime compound can be used individually or in combination of 2 or more types.

（Ｒ^１は水素原子、ニトロ基又は１価の有機基であり、Ｒ^２及びＲ^３は、それぞれ、鎖状アルキル基、環状炭化水素基、又はヘテロアリール基であり、Ｒ^２とＲ^３とは相互に結合してスピロ環を形成してもよく、Ｒ^４は１価の有機基であり、Ｒ^５は、水素原子、置換基を有してもよい炭素原子数１〜１１のアルキル基、又は置換基を有してもよいアリール基であり、ｍは０又は１である。）

(R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, R ² and R ³ are each a chain alkyl group, a cyclic hydrocarbon group, or a heteroaryl group, and R ² and R ³ are ^May combine with each other to form a spiro ring, R ⁴ is a monovalent organic group, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 11 carbon atoms that may have a substituent. Or an aryl group which may have a substituent, and m is 0 or 1.)

  It is considered that an interaction occurs between the oxime compound and the colorant, and the oxime compound can improve the dispersion stability of the colorant. In particular, when the colorant is a pigment made of a nitrogen-containing aromatic ring compound, it is considered as follows. In a pigment made of a nitrogen-containing aromatic ring compound, the π-electron system is unstable due to the influence of the nitrogen atom contained in the molecule as compared with the case where no nitrogen atom is contained. Therefore, a pigment made of a nitrogen-containing aromatic ring compound is unlikely to have good dispersion stability. The oxime compound used in the pigment dispersion according to the present invention contains an oxime group and a carbonyl group, and further, an aromatic ring is bonded to these groups, so that a stable π electron system is formed. It is presumed that a π-π interaction occurs between the oxime compound and the pigment composed of the nitrogen-containing aromatic ring compound, the molecules of each other are stacked, and the π electron system of the pigment is stabilized. As a result, it is considered that the oxime compound can improve the dispersion stability of a pigment composed of a nitrogen-containing aromatic ring compound.

  The oxime compound can be suitably used as a dispersion aid, particularly as a dispersion aid for dispersing a colorant.

In Formula (1), R ¹ is a hydrogen atom, a nitro group, or a monovalent organic group. R ¹ is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by — (CO) _m — on the fluorene ring in the formula (1). In formula (1), the bonding position of R ^{1 to} the fluorene ring is not particularly limited. The bonding position of R ^{1 to} the fluorene ring is preferably the 2-position in the fluorene ring because the synthesis of the compound represented by formula (1) is easy.

When R ¹ is an organic group, R ¹ is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Preferable examples when R ¹ is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. An optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a substituent An optionally substituted naphthoxycarbonyl group, an optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, a substituted Examples include a heterocyclylcarbonyl group which may have a group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

When R ¹ is an alkyl group, number of carbon atoms in the alkyl group is preferably from 1 to 20, 1 to 6 is more preferable. Further, when R ¹ is an alkyl group, it may be linear or branched. Specific examples in the case where R ¹ is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. When R ¹ is an alkyl group, the alkyl group may include an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

If R ¹ is an alkoxy group, number of carbon atoms in the alkoxy group is preferably from 1 to 20, 1 to 6 is more preferable. Further, when R ¹ is an alkoxy group, it may be linear or branched. Specific examples when R ¹ is an alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octoxyl group, Examples thereof include a tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, and an isodecyloxy group. When R ¹ is an alkoxy group, the alkoxy group may contain an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

When R ¹ is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 to 10, and more preferably 3 to 6. Specific examples of when R ¹ is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples when R ¹ is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ¹ is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, and more preferably 2 to 7. Specific examples when R ¹ is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecane Examples include a noyl group and an n-hexadecanoyl group. Specific examples when R ¹ is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

When R ¹ is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2-20, and more preferably 2-7. Specific examples in the case where R ¹ is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, i Examples include a sononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

When R ¹ is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 to 20, and more preferably 7 to 10. Moreover, when R < ¹ > is a naphthyl alkyl group, 11-20 are preferable and, as for the carbon atom number of a naphthyl alkyl group, 11-14 are more preferable. Specific examples when R ¹ is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples in the case where R ¹ is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2- (α-naphthyl) ethyl group, and a 2- (β-naphthyl) ethyl group. . When R ¹ is a phenylalkyl group or a naphthylalkyl group, R ¹ may further have a substituent on the phenyl group or naphthyl group.

When R ¹ is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, and O, such monocycles, or such monocycles and benzene rings are condensed. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline. When R ¹ is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ¹ is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R ¹ is a heterocyclyl group.

When R ¹ is an amino group substituted with an organic group having 1 or 2, suitable examples of the organic group include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, and carbon atoms. A saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl having 7 to 20 carbon atoms which may have a substituent A naphthyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group, and the like. . Specific examples of these suitable organic groups are the same as those for R ¹ . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

In the case where the phenyl group, naphthyl group, and heterocyclyl group included in R ¹ further have a substituent, the substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a carbon atom. A monoalkylamino group having a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms And a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group included in R ¹ further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ¹ have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, R ¹ is preferably a nitro group or a group represented by R ⁶ —CO— because the sensitivity tends to be improved. R ⁶ is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Examples of a group suitable as R ⁶ include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Or a heterocyclyl group that may be used. Among these groups, R ⁶ is particularly preferably a 2-methylphenyl group, a thiophen-2-yl group, or an α-naphthyl group.
Moreover, it is preferable that R ¹ is a hydrogen atom because transparency tends to be good. When R ¹ is a hydrogen atom and R ⁴ is (R4-2) described later, the transparency tends to be better.

In Formula (1), R ² and R ³ are each a chain alkyl group, a cyclic hydrocarbon group, or a heteroaryl group. Among these groups, R ² and R ³ are preferably chain alkyl groups.

When R ² and R ³ are chain alkyl groups, the chain alkyl group may be a linear alkyl group or a branched alkyl group. When R ² and R ³ are chain alkyl groups, the chain alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms. Further, when R ¹ is an alkyl group, it may be linear or branched. Specific examples in the case where R ¹ is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. When R ¹ is an alkyl group, the alkyl group may include an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ² and R ³ are cyclic hydrocarbon groups, the cyclic hydrocarbon group may be an aliphatic cyclic hydrocarbon group or an aromatic cyclic hydrocarbon group.

When R ² and R ³ are aromatic cyclic hydrocarbon groups, the aromatic cyclic hydrocarbon group is a phenyl group or a group formed by bonding a plurality of benzene rings via a carbon-carbon bond. It is preferably a group formed by condensation of a plurality of benzene rings. When the aromatic cyclic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of benzene rings included in the aromatic cyclic hydrocarbon group is particularly limited. 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Preferable specific examples of the aromatic cyclic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

When R ² and R ³ are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. Although the carbon atom number of an aliphatic cyclic hydrocarbon group is not specifically limited, 3-20 are preferable and 3-10 are more preferable. Examples of monocyclic cyclic hydrocarbon groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, Examples include a tetracyclododecyl group and an adamantyl group.

When R ² and R ³ are heteroaryl groups, the heteroaryl group is a 5- or 6-membered monocycle containing one or more N, S, O, such monocycles, or such monocycles It is a heteroaryl group condensed with a benzene ring. When the heteroaryl group is a condensed ring, the number of rings is limited to 3. Examples of the heterocyclic ring constituting the heteroaryl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indole. , Isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline and the like.

R ² and R ³ may be bonded to each other to form a spiro ring. The group consisting of a spiro ring formed by R ² and R ³ is preferably a cycloalkylidene group. When R ² and R ³ are combined to form a cycloalkylidene group, the spiro ring constituting the cycloalkylidene group is preferably a 5-membered ring to a 6-membered ring, and more preferably a 5-membered ring. .

When the group formed by combining R ² and R ³ is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring that may be condensed with the cycloalkylidene group include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, pyridine A ring, a pyrazine ring, and a pyrimidine ring.

Examples of suitable organic groups for R ⁴ include, similarly to R ¹ , an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a substituent A good benzoyloxy group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, An optionally substituted naphthoxycarbonyl group, an optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group, and an optionally substituted heterocyclyl group An optionally substituted heterocyclyl group, 1, or an amino group substituted with two organic groups, morpholin-1-yl group, and piperazine-1-yl group. Specific examples of these groups are the same as those described for R ¹ . R ⁴ is also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, or a phenylthioalkyl group optionally having a substituent on the aromatic ring. The substituent that the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent that the phenyl group contained in R ¹ may have.

Among organic groups, as R ⁴ , an alkyl group, a cycloalkyl group, an optionally substituted phenyl group, or a cycloalkylalkyl group, an optionally substituted phenylthio group on an aromatic ring. Alkyl groups are preferred. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. Among the phenyl groups that may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. 1-8 are preferable, as for the carbon atom number of the alkylene group contained in a cycloalkylalkyl group, 1-4 are more preferable, and 2 is especially preferable. Of the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. 1-8 are preferable, as for the carbon atom number of the alkylene group contained in the phenylthioalkyl group which may have a substituent on an aromatic ring, 1-4 are more preferable, and 2 is especially preferable. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2- (4-chlorophenylthio) ethyl group is preferable.

（式（Ｒ４−１）及び（Ｒ４−２）中、Ｒ^６及びＲ^７はそれぞれ有機基であり、ｐは０〜４の整数であり、Ｒ^６及びＲ^７がベンゼン環上の隣接する位置に存在する場合、Ｒ^６とＲ^７とが互いに結合して環を形成してもよく、ｑは１〜８の整数であり、ｒは１〜５の整数であり、ｓは０〜（ｒ＋３）の整数であり、Ｒ^８はアルキル基である。） Having described ^{R 4,} as is ^{R 4,} preferably a group represented by the following formula (R4-1) or (R4-2).

(In formulas (R4-1) and (R4-2), R ⁶ and R ⁷ are each an organic group, p is an integer of 0 to 4, and R ⁶ and R ⁷ are adjacent positions on the benzene ring. R ⁶ and R ⁷ may be bonded to each other to form a ring, q is an integer of 1 to 8, r is an integer of 1 to 5, and s is 0 to (r + 3). ) And R ⁸ is an alkyl group.)

Examples of the organic group for R ⁶ and R ^{7 in} formula (R4-1) are the same as those for R ¹ . R ⁶ is preferably an alkyl group or a phenyl group. When R ⁶ is an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, R ⁶ is most preferably a methyl group. When R ⁶ and R ⁷ are combined to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferable examples of the group represented by the formula (R4-1) in which R ⁶ and R ⁷ form a ring include a naphthalen-1-yl group, 1, 2, 3, 4-tetrahydronaphthalen-5-yl group etc. are mentioned. In said formula (R4-1), p is an integer of 0-4, it is preferable that it is 0 or 1, and it is more preferable that it is 0.

In the above formula (R4-2), ^{R 8} is an alkyl group. 1-10 are preferable, as for the carbon atom number of an alkyl group, 1-5 are more preferable, and 1-3 are especially preferable. As R ⁸ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.

  In said formula (R4-2), r is an integer of 1-5, the integer of 1-3 is preferable and 1 or 2 is more preferable. In said formula (R4-2), s is 0- (r + 3), the integer of 0-3 is preferable, the integer of 0-2 is more preferable, and 0 is especially preferable. In said formula (R4-2), q is an integer of 1-8, the integer of 1-5 is preferable, the integer of 1-3 is more preferable, and 1 or 2 is especially preferable.

In Formula (1), R ⁵ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. Preferred examples of the substituent that may be present when R ⁵ is an alkyl group include a phenyl group and a naphthyl group. In addition, preferred examples of the substituent that R ¹ may have when it is an aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

In formula (1), preferred examples of R ⁵ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, and a naphthyl group. Among these, a methyl group or a phenyl group is more preferable.

When m is 0, the compound represented by the general formula (1) can be synthesized according to the following scheme 1, for example. In Scheme 1, a fluorene derivative represented by the following formula (1-1) is used as a raw material. When R ¹ is a nitro group or a monovalent organic group, the fluorene derivative represented by the formula (1-1) is converted into a fluorene derivative substituted at the 9-position with R ² and R ³ by a known method, It can be obtained by introducing the substituent R ¹ . The fluorene derivative substituted at the 9-position with R ² and R ³ is, for example, an alkali metal hydroxide as described in JP-A-06-234668 when R ² and R ³ are alkyl groups. It can be obtained by reacting fluorene with an alkylating agent in the presence of an aprotic polar organic solvent. In addition, an alkylating agent such as an alkyl halide, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide are added to an organic solvent solution of fluorene. By performing the alkylation reaction, 9,9-alkyl-substituted fluorene can be obtained.

  The fluorene derivative represented by the formula (1-1) is acylated by the Friedel-Crafts reaction using the halocarbonyl compound represented by the formula (1-2), and represented by the formula (1-3). A fluorene derivative is obtained. In formula (1-2), Hal is a halogen atom. The position acylated by the compound represented by the formula (1-2) on the fluorene ring can be changed by appropriately changing the conditions of the Friedel-Crafts reaction, or the compound represented by the formula (1-2) on the fluorene ring. It can be selected by a method in which protection and deprotection are performed at other positions to be acylated by.

Next, the resulting fluorene derivative represented by the formula (1-3) is oximed with hydroxylamine to obtain an oxime compound represented by the following formula (1-4). An oxime compound of the formula (1-4) and an acid anhydride ((R ⁵ CO) ₂ O) represented by the following formula (1-5) or an acid halide represented by the following general formula (1-6) A compound represented by the following formula (1-7) can be obtained by reacting (R ⁵ COHal, Hal is a halogen atom).

In the formulas (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), and (1-7), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are the same as those in the formula (1).

<Scheme 1>

When m is 1, the compound represented by the formula (1) can be synthesized, for example, according to the following scheme 2. In Scheme 2, a fluorene derivative represented by the following formula (2-1) is used as a raw material. The fluorene derivative represented by the formula (2-1) is obtained by acylating the compound represented by the formula (1-1) by a Friedel-Crafts reaction in the same manner as in Scheme 1. A nitrite ester (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following general formula (2-2) in the presence of hydrochloric acid is added to the fluorene derivative represented by the formula (2-1). By reacting, a ketoxime compound represented by the following formula (2-3) is obtained. Next, a ketoxime compound represented by the following formula (2-3) and an acid anhydride ((R ⁵ CO) ₂ O) represented by the following formula (2-4), or the following general formula (2-5) A compound represented by the following formula (2-6) can be obtained by reacting with an acid halide represented by the formula (R ⁵ COHal, Hal is a halogen atom). In the following formulas (2-1), (2-3), (2-4), (2-5), and (2-6), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ is the same as in the general formula (1).
When m is 1, there exists a tendency which can reduce more the generation | occurrence | production of the foreign material in the pattern formed using the photosensitive composition containing the compound represented by Formula (1).

<Scheme 2>

Preferable specific examples of the compound represented by the formula (1) include the following compounds.

  In the colorant dispersion according to the present invention, the content of the oxime compound is not particularly limited as long as the object of the present invention is not impaired. The content of the oxime compound is typically preferably 1 to 50 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the colorant. By setting the content of the oxime compound in such a range, the dispersion stability of the colorant tends to be good in the obtained colorant dispersion. In addition, the colorant dispersion in which the content of the oxime compound is within the above range is preferably used for preparing a photosensitive resin composition capable of forming a highly adhesive micropattern with a low exposure amount. Can do.

  In the colorant dispersion according to the present invention, the total content of the dispersant and the oxime compound is preferably 1 to 60 parts by mass with respect to 100 parts by mass of the colorant, and 1 to 55 parts by mass. More preferably, it is 1 to 20 parts by mass. When the total content is in the above range, the colorant dispersion and the colorant dispersion are secured while ensuring uniform dispersion of the colorant and the effect of the oxime compound in the colorant dispersion according to the present invention. In the photosensitive resin composition obtained from the above, the balance of each component tends to be good. Moreover, since the compounding quantity of the other component in the said photosensitive resin composition can be increased relatively, so that an upper limit is small, it becomes easy to improve other characteristics, such as a sensitivity.

[solvent]
Examples of the solvent in the colorant dispersion according to the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. , Diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene Glycol mono-n-butyl ether, dipropylene glycol (Poly) alkylene glycol mono, such as dimonomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether Alkyl ethers: (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Acetates; Other ethers such as ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate Alkyl lactates such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, Hydroxyethyl acetate, 2-hydroxy-3-methyl methyl carbonate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropio Nate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate , Other esters such as methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone Amides such as N, N-dimethylformamide and N, N-dimethylacetamide. A solvent can be used individually or in combination of 2 or more types.

  Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, and 3-methoxybutyl acetate are alkali-soluble as described below. The resin, photopolymerizable monomer, photopolymerization initiator, and the compound represented by the above formula (1) exhibit excellent solubility and are preferable because the dispersibility of the colorant can be improved. It is particularly preferable to use propylene glycol monomethyl ether acetate or 3-methoxybutyl acetate.

  The amount of the solvent is preferably such that the solid content concentration of the colorant dispersion according to the present invention is 1 to 50% by mass, and more preferably 5 to 30% by mass.

[Dispersion aids other than oxime compounds]
The colorant dispersion according to the present invention may contain a dispersion aid other than the oxime compound as an optional component. The dispersion aid other than the oxime compound is preferably a dispersion aid having a nitrogen-containing aromatic ring in terms of stacking properties, for example, using a photosensitive resin composition described later, and adhesion to a substrate, It is preferable that it is a silane coupling agent which has a nitrogen-containing aromatic ring at the point which can form a pattern with favorable water resistance. Specifically as a silane coupling agent which has a nitrogen-containing aromatic ring, what is represented by following formula (11) is preferable.

R ¹¹ _p R ¹² _(3-p) Si—R ¹³ —NH—C (O) —Y—R ¹⁴ —X (11)
(In Formula (11), R ¹¹ is an alkoxy group, R ¹² is an alkyl group, p is an integer of 1 to 3, R ¹³ is an alkylene group, and Y is —NH— or —O—. Or -S-, R ¹⁴ is a single bond or an alkylene group, X is a nitrogen-containing heteroaryl group which may have a substituent and may be monocyclic or polycyclic, The ring bonded to —Y—R ¹⁴ — is a nitrogen-containing 6-membered aromatic ring, and —Y—R ¹⁴ — is bonded to the carbon atom in the nitrogen-containing 6-membered aromatic ring.

In formula (11), R ¹¹ is an alkoxy group. For R ^11, number of carbon atoms in the alkoxy group 1 to 6, more preferably 1 to 4, from the viewpoint of the reactivity of the silane coupling agent 1 or 2 are particularly preferred. Preferable specific examples of R ¹¹ include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, and n. -A hexyloxy group is mentioned. Among these alkoxy groups, a methoxy group and an ethoxy group are preferable.

The silanol group produced by hydrolysis of R ^11, which is an alkoxy group, reacts with the surface of the substrate and the like, thereby improving the adhesion of the pattern formed using the photosensitive resin composition described later to the substrate surface. . For this reason, p is preferably 3 from the viewpoint of easily improving the adhesion of the pattern to the substrate surface.

In formula (11), R ¹² is an alkyl group. For R ^12, the number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, from the viewpoint of the reactivity of the silane coupling agent 1 or 2 are particularly preferred. Preferable specific examples of R ¹² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. N-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group.

In formula (11), R ¹³ is an alkylene group. For R ^13, the number of carbon atoms in the alkylene group is preferably 1 to 12, more preferably 1 to 6, 2 to 4 are particularly preferred. Preferred examples of R ¹³ include methylene group, 1,2-ethylene group, 1,1-ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, propane-1,1- Diyl group, propane-2,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-1,2-diyl group, butane-1,1-diyl group, butane- 2,2-diyl group, butane-2,3-diyl group, pentane-1,5-diyl group, pentane-1,4-diyl group, hexane-1,6-diyl group, heptane-1,7- And diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, and dodecane-1,12-diyl group. It is done. Among these alkylene groups, 1,2-ethylene group, propane-1,3-diyl group, and butane-1,4-diyl group are preferable.

  Y is —NH—, —O—, or —S—, and is preferably —NH—. Since the bond represented by -CO-NH- is less susceptible to hydrolysis than the bond represented by -CO-O- or -CO-S-, Y in the photosensitive resin composition described later is- When a silane coupling agent that is NH- is used, a pattern having excellent water resistance can be easily formed.

R ¹⁴ is a single bond or an alkylene group, and preferably a single bond. Preferable examples when R ¹⁴ is an alkylene group are the same as those for R ¹³ .

X is a nitrogen-containing heteroaryl group which may have a substituent and may be monocyclic or polycyclic, and the ring bonded to —Y—R ¹⁴ — in X is a nitrogen-containing 6-membered aromatic ring, -YR ¹⁴ -is bonded to a carbon atom in the nitrogen-containing 6-membered aromatic ring. The reason is unknown, but when a silane coupling agent having such X in the photosensitive resin composition described later is used, a pattern having excellent adhesion to the substrate and water resistance can be formed.

  When X is a polycyclic heteroaryl group, the heteroaryl group may be a group in which a plurality of monocycles are condensed or a group in which a plurality of monocycles are bonded via a single bond. When X is a polycyclic heteroaryl group, the number of rings contained in the polycyclic heteroaryl group is preferably 1 to 3. When X is a polycyclic heteroaryl group, the ring condensed or bonded to the nitrogen-containing 6-membered aromatic ring in X may or may not contain a hetero atom, and may be an aromatic ring or an aromatic ring. It does not have to be a ring.

  Examples of the substituent that X which is a nitrogen-containing heteroaryl group may have include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, C2-C6 alkenyloxy group, C2-C6 aliphatic acyl group, benzoyl group, nitro group, nitroso group, amino group, hydroxy group, mercapto group, cyano group, sulfonic acid group, carboxyl group And halogen atoms. The number of substituents X has is not particularly limited as long as the object of the present invention is not impaired. The number of substituents X has is preferably 5 or less, more preferably 3 or less. When X has a plurality of substituents, the plurality of substituents may be the same or different.

Preferable examples of X include groups represented by the following formula.

Among the above groups, a group of the following formula is more preferable as X.

Preferable specific examples of the compound represented by the formula (11) described above include the following compounds.

  In the colorant dispersion according to the present invention, the content of the dispersion aid other than the oxime compound is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass.

[Method for preparing colorant dispersion]
In the colorant dispersion according to the present invention, the colorant, the dispersant, the oxime compound, and the solvent are mixed (dispersed and kneaded) with a stirrer such as a three-roll mill, a ball mill, or a sand mill. It can be prepared by filtering with a filter such as a 5 μm membrane filter. In the preparation of the colorant dispersion, the colorant and the oxime compound (as a dispersion aid) are mixed (dispersed and kneaded) together with a stirrer, so that the colorant and the oxime compound are mixed. Thus, it is considered that interaction occurs and the effect of the present invention can be obtained. In particular, when the colorant is a pigment comprising a nitrogen-containing aromatic ring compound, in the preparation of the colorant dispersion, the pigment comprising a nitrogen-containing aromatic ring compound and the oxime compound (as a dispersion aid) By mixing (dispersing and kneading) both with a stirrer, a π-π interaction occurs between the pigment comprising the nitrogen-containing aromatic ring compound and the oxime compound, and the effects of the present invention are obtained. Conceivable.

<Photosensitive resin composition>
The photosensitive resin composition according to the present invention contains at least a base resin, a photopolymerization initiator, and a colorant dispersion according to the present invention.

[Base resin]
It does not specifically limit as base resin, The well-known resin generally used in the photosensitive resin composition is mentioned. Base resin can be used individually or in combination of 2 or more types.

  Examples of the base resin include polymerizable resins such as polymerizable group-containing resins. Examples of such polymerizable resins include those having an ethylenically unsaturated group among the alkali-soluble resins described later.

  Moreover, alkali-soluble resin is mentioned as base resin. The alkali-soluble resin is a resin film having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate), and a 1 μm-thick resin film is formed on the substrate and placed in a 0.05% by mass KOH aqueous solution for 1 minute. When immersed, it means a film that dissolves 0.01 μm or more in thickness.

  The alkali-soluble resin is not particularly limited as long as it is a resin exhibiting alkali solubility as described above, and a conventionally known alkali-soluble resin can be used. The alkali-soluble resins can be used alone or in combination of two or more.

  An example of a suitable alkali-soluble resin is (A1) a resin having a cardo structure. (A1) The resin having a cardo structure is not particularly limited, and conventionally known resins can be used. Among these, the resin represented by the following formula (a-1) is preferable.

In the formula ^{(a-1), X} a represents a group represented by the following formula (a-2).

In the above formula (a-2), each R ^a1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, each R ^a2 independently represents a hydrogen atom or a methyl group, W ^a represents a single bond or a group represented by the following formula (a-3).

In the formula (a-1), Y ^a represents a residue obtained by removing an acid anhydride group (—CO—O—CO—) from a dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride and glutaric anhydride.

Further, in the above formula ^(a-1), Z a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like.
Moreover, in said formula (a-1), m shows the integer of 0-20.

  (A1) The mass average molecular weight of the resin having a cardo structure is preferably 1000 to 40000, and more preferably 2000 to 30000. By setting it as the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.

  Moreover, (A2) epoxy resin is mentioned as another example of suitable alkali-soluble resin. (A2) The epoxy resin is not particularly limited, and a conventionally known epoxy resin can be used, and it has an ethylenically unsaturated group even if it does not have an ethylenically unsaturated group. It may be.

  As an epoxy resin not having an ethylenically unsaturated group, for example, a resin (A2-1) obtained by at least copolymerizing an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound can be used.

Examples of unsaturated carboxylic acids include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; It is done. Among these, (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the resulting resin, availability, and the like. These unsaturated carboxylic acids can be used alone or in combination of two or more.
In the present specification, “(meth) acrylic acid” means both acrylic acid and methacrylic acid.

  The proportion of the structural unit derived from the unsaturated carboxylic acid (the structural unit having a carboxyl group) in the resin (A2-1) is preferably 5 to 29% by mass, more preferably 10 to 25% by mass. preferable. By setting it as the said range, the developability of the photosensitive resin composition can be made moderate.

  The epoxy group-containing unsaturated compound may have no alicyclic epoxy group or may have an alicyclic epoxy group, but more preferably has an alicyclic epoxy group.

  Examples of the epoxy group-containing unsaturated compound having no alicyclic epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 6,7-epoxyheptyl. (Meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate and other (meth) acrylic acid epoxy alkyl esters; α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylic acid Α-alkylacrylic acid epoxy alkyl esters such as glycidyl and α-ethylacrylic acid 6,7-epoxyheptyl; glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether ;etc Is mentioned. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o-vinylbenzyl from the viewpoints of copolymerization reactivity, strength of cured resin, and the like. Glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferred.

  The alicyclic group of the epoxy group-containing unsaturated compound having an alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

  Specifically, examples of the epoxy group-containing unsaturated compound having an alicyclic epoxy group include compounds represented by the following formulas (a4-1) to (a4-16). Among these, in order to make the developability of the photosensitive resin composition appropriate, compounds represented by the following formulas (a4-1) to (a4-6) are preferable, and the following formula (a4-1) The compound represented by (a4-4) is more preferable.

In the above formula, R ^a3 represents a hydrogen atom or a methyl group, R ^a4 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a5 represents a divalent hydrocarbon having 1 to 10 carbon atoms. Represents a group, and n represents an integer of 0 to 10. R ^a4 is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^a5 , for example, methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, phenylene group, cyclohexylene group, —CH ₂ —Ph—CH ₂ — (Ph is A phenylene group) is preferred.

  These epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

  The proportion of the structural unit derived from the epoxy group-containing unsaturated compound (structural unit having an epoxy group) in the resin (A2-1) is preferably 5 to 90% by mass, and 15 to 75% by mass. Is more preferable. By setting it as the above range, it becomes easy to form a color filter having a good shape.

  The resin (A2-1) is preferably obtained by further copolymerizing an alicyclic group-containing unsaturated compound.

  The alicyclic group of the alicyclic group-containing unsaturated compound may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

  Specifically, examples of the alicyclic group-containing unsaturated compound include compounds represented by the following formulas (a5-1) to (a5-8). Among these, in order to make the developability of the photosensitive resin composition appropriate, compounds represented by the following formulas (a5-3) to (a5-8) are preferable, and the following formula (a5-3) , (A5-4) is more preferable.

In the above formula, R ^a6 represents a hydrogen atom or a methyl group, R ^a7 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a8 represents a hydrogen atom or 1 to 5 carbon atoms. Represents an alkyl group. R ^a7 is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^a8 , for example, a methyl group and an ethyl group are preferable.

  The proportion of the structural unit derived from the alicyclic group-containing unsaturated compound in the resin (A2-1) is preferably 1 to 40% by mass, and more preferably 5 to 30% by mass.

  Further, the resin (A2-1) may be obtained by further copolymerizing other compounds than the above. Examples of such other compounds include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds can be used alone or in combination of two or more.

  As (meth) acrylic acid esters, linear or branched chain such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate, etc. Alkyl (meth) acrylates; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (Meth) acrylate; etc. are mentioned.

  (Meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (meth) acrylamide, N -Methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide and the like.

  Examples of the allyl compound include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Can be mentioned.

  As vinyl ethers, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether , Alkyl vinyl ethers such as diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichloropheny And the like; ethers, vinyl naphthyl ether, vinyl aryl ethers such as vinyl anthranyl ether.

  Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl vinyl. Examples include enyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

  Styrenes include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy Alkyl styrene such as methyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl Styrene, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.

  The mass average molecular weight of the resin (A2-1) is preferably 2000 to 50000, and more preferably 5000 to 30000. By setting it as the above range, there is a tendency that the film forming ability and developability of the photosensitive resin composition are easily balanced.

  On the other hand, as an epoxy resin having an ethylenically unsaturated group, for example, a carboxyl group of a resin obtained by polymerizing at least an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound, and an epoxy group of an epoxy group-containing unsaturated compound A resin (A2-2) obtained by reacting an unsaturated carboxylic acid and an epoxy group of a resin obtained by polymerizing at least an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound, and a carboxyl group of an unsaturated carboxylic acid. Resin (A2-3) obtained by reacting can be used.

  As unsaturated carboxylic acid and an epoxy group containing unsaturated compound, the compound illustrated by the said resin (A2-1) is mentioned. Therefore, the resin (A2-1) is exemplified as a resin obtained by polymerizing at least an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound.

  The proportion of the structural unit derived from the unsaturated carboxylic acid (the structural unit having a carboxyl group) in the resins (A2-2) and (A2-3) is preferably 5 to 60% by mass, and 10 to 40% by mass. % Is more preferable. By setting it as the said range, the developability of the photosensitive resin composition can be made moderate.

  Moreover, it is preferable that the ratio of the structural unit (structural unit which has an epoxy group) derived from the epoxy group containing unsaturated compound in the said resin (A2-2) and (A2-3) is 5-90 mass%, More preferably, it is 15-75 mass%. By setting it as the above range, it becomes easy to form a color filter having a good shape.

  The mass average molecular weight of the resins (A2-2) and (A2-3) is preferably 2000 to 50000, and more preferably 5000 to 30000. By setting it as the above range, there is a tendency that the film forming ability and developability of the photosensitive resin composition are easily balanced.

  In addition to the above, (A2) epoxy resin includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, An epoxy (meth) acrylate resin obtained by reacting an epoxy group of an epoxy resin such as a polycarboxylic acid polyglycidyl ester, a polyol polyglycidyl ester, an amine epoxy resin, or a dihydroxybenzene type epoxy resin with (meth) acrylic acid, etc. It can also be used.

  The content of the base resin is preferably 40 to 85% by mass and more preferably 45 to 75% by mass with respect to the solid content of the photosensitive resin composition. By setting it as the above range, there is a tendency that developability is easily balanced.

[Photopolymerization initiator]
It does not specifically limit as a photoinitiator, A conventionally well-known photoinitiator can be used. A photoinitiator can be used individually or in combination of 2 or more types.

  Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, bis (4-dimethylaminophenyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4- Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- ( o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobu Tyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- ( o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4 ' -Bisdimethylaminobenzophenone (ie Michler's ketone), 4,4 -Bisdiethylaminobenzophenone (ie ethyl Michler's ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin- n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethyl Aminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) ) Heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (Furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-tri 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl]- 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo -4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trick Loromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, ethanone, 1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 1,2-octanedione, 1- [4- (phenylthio)- , 2- (O-benzoyloxime)], 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, “NCI-831” (trade name: manufactured by ADEKA), and the like. The oxime compound used in the present invention can also be used as a photopolymerization initiator. That is, in the photosensitive resin composition according to the present invention, the oxime compound is contained as a dispersion aid (included as a dispersion aid in the colorant dispersion), but is further contained as a photopolymerization initiator. It may be. In this case, the oxime compound as the photopolymerization initiator is considered to have no interaction with the colorant. In particular, when the colorant is a pigment made of a nitrogen-containing aromatic ring compound, the oxime compound as the photopolymerization initiator has no π-π interaction with the pigment made of the nitrogen-containing aromatic ring compound. Conceivable. About the oxime compound as a photoinitiator, it is the same as the above, and the compound represented by the said Formula (1) is preferable.

It is preferable that content of a photoinitiator is 0.5-20 mass% with respect to solid content of the photosensitive resin composition. By setting it as said range, sufficient heat resistance and chemical-resistance can be acquired, a coating-film formation ability can be improved, and hardening failure can be suppressed.
Moreover, when the photosensitive resin composition contains the said oxime compound as a photoinitiator, it is preferable that the ratio of the said oxime compound is 1-100 mass% with respect to the total amount of a photoinitiator, 20-100. More preferably, it is 50 mass%, It is still more preferable that it is 50-100 mass%, It is especially preferable that it is 80-100 mass%. By setting it as the said range, the sensitivity and fine wire adhesiveness of the photosensitive resin composition can be improved.

[Colorant dispersion]
The content of the colorant dispersion according to the present invention may be appropriately determined according to the use of the photosensitive resin composition. As an example, the content of the colorant in the photosensitive resin composition is the photosensitive resin composition. The amount of 5 to 70% by mass with respect to the solid content is preferable, and the amount of 25 to 60% by mass is more preferable.

  Furthermore, when using the photopolymerizable monomer described later, the content of the colorant dispersion according to the present invention is the sum of the content of the oxime compound in the photosensitive resin composition and the base resin and the photopolymerizable monomer. The amount of 0.01 to 2.5 parts by mass is preferable with respect to 100 parts by mass of the amount, and the amount of 0.01 to 0.5 parts by mass is more preferable. By adjusting the content of the colorant dispersion according to the present invention so that the content of the oxime compound in the photosensitive resin composition falls within this range, it becomes easy to form a fine pattern having excellent adhesion to the substrate. .

[Photopolymerizable monomer]
The photosensitive resin composition according to the present invention may contain a photopolymerizable monomer. It does not specifically limit as a photopolymerizable monomer, A conventionally well-known monofunctional monomer and a polyfunctional monomer can be used. A photopolymerizable monomer can be used individually or in combination of 2 or more types.

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

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

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

[Other ingredients]
The said photosensitive resin composition may contain various additives as needed. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, and a surfactant.

<Method for producing photosensitive resin composition>
The method for producing a photosensitive resin composition according to the present invention includes at least a step of mixing the base resin, the photopolymerization initiator, and the colorant dispersion according to the present invention. In this step, in addition to the above components, a photopolymerizable monomer and / or other components may be mixed. These components can be mixed with a stirrer such as a three-roll mill, a ball mill, or a sand mill. In addition, you may filter using filters, such as a 5 micrometer membrane filter, so that the manufactured photosensitive resin composition may become uniform.

  In the method for producing a photosensitive resin composition according to the present invention, a colorant, a dispersant, the oxime compound, and a solvent are mixed in advance to prepare a colorant dispersion, and the colorant dispersion is used as a base resin. Etc. with other ingredients. By passing through such a process, the photosensitive resin composition which can form a highly adhesive micro pattern even with a low exposure amount is obtained.

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

  In the following examples and comparative examples, the following compounds 1 to 3 and comparative compounds 1 and 2 were used as oxime compounds.

<Synthesis of oxime compounds>
Hereinafter, the synthesis of Compounds 1 to 3 will be described by Synthesis Examples 1 to 4.

[Synthesis Example 1]
(Synthesis of 9,9-di-n-propylfluorene)
6.64 g (40 mmol) of fluorene was dissolved in 27 mL of THF. To the obtained solution, 0.12 g (1.1 mmol) of potassium tert-butoxide, 12.30 g (100 mmol) of 1-bromopropane, and 27 mL of a 50% strength by weight aqueous sodium hydroxide solution were gradually added under a nitrogen atmosphere. did. The resulting mixture was stirred at 80 ° C. for 3 hours for reaction. After adding 33 g of ethyl acetate and 33 g of water to the mixture after the reaction, the mixture was separated into an organic layer and an aqueous layer. The obtained organic layer was dehydrated with anhydrous sodium sulfate, and then the solvent was removed from the organic layer using a rotary evaporator to obtain 8.32 g (yield 83%) of 9,9-di-n-propylfluorene. .

[Synthesis Example 2]
(Synthesis of 2-nitro-9,9-di-n-propylnitrofluorene)
To a mixed solvent composed of 131 mL of acetic acid and 262 mL of acetic anhydride, 9.18 g (40 mmol) of copper (II) dinitrate trihydrate was added, and the mixed solvent was stirred for 10 minutes. Thereafter, a solution obtained by dissolving 10.02 g (40 mmol) of 9,9-di-n-propylfluorene obtained in the method of Synthesis Example 1 in 131 mL of acetic acid was slowly added to the mixed solvent in several portions. Next, the mixed solvent containing 9,9-di-n-propylfluorene was stirred for 3 hours to perform a nitration reaction. After the reaction, the reaction mixture was poured into a beaker containing ice water. The deposited precipitate was collected by filtration, and then washed with water and dried to obtain 10.76 g of 2-nitro-9,9-di-n-propylfluorene (yield 91%).

[Synthesis Example 3]
(Synthesis of Compound 1)
In the presence of 2.62 g of aluminum chloride, 4.10 g (16.37 mmol) of 9,9-di-n-propylfluorene and 3.04 g (18.00 mmol) of (2-methylphenyl) acetic acid chloride were added. The reaction was carried out in 50 ml of dichloromethane solvent for 1 hour under ice cooling. The reaction mixture was poured into ice water and the organic layer was separated. The collected organic layer was dried over anhydrous magnesium sulfate and evaporated. The residue was purified by a silica gel column with an eluent of ethyl acetate / hexane = 1/2 to obtain 5.95 g (15.55 mmol) of 2- (2-methylphenyl) acetyl-9,9-di-n-propylcarbazole. It was. 2- (2-methylphenyl) acetyl-9,9-di-n-propylcarbazole 5.95 g (15.55 mmol), 1.60 g (15.55 mmol) of concentrated hydrochloric acid, and 2.42 g of isobutyl nitrite ( In the presence of 23.33 mmol), the reaction was carried out in 25 ml of dimethylformamide solvent under ice cooling for 3 hours. The reaction mixture was evaporated, ethyl acetate was added to the residue, washed with saturated brine, dried over anhydrous magnesium sulfate and evaporated to 2- [2-methylphenyl (hydroxyimino) acetyl] -9,9-di 4.80 g (11.67 mmol) of n-propylcarbazole was obtained. 2- [2-Methylphenyl (hydroxyimino) acetyl] -9,9-di-n-propylcarbazole 4.80 g (11.67 mmol), acetic anhydride 1.43 g (13.42 mmol), and triethylamine 1.36 g (13.42 mmol) and 45.00 ml of dimethylformamide solvent were mixed and stirred at 35 ° C. for 3 hours. After cooling to room temperature, ethyl acetate was added to the reaction solution, washed with water, dried over anhydrous magnesium sulfate and evaporated. The residue was purified by a silica gel column with an eluent of ethyl acetate / hexane = 2/1 to obtain compound 1, 4.76 g (10.50 mmol, yield 72%). ¹ H-NMR measurement results of Compound 1 were as follows.
¹ H-NMR (600 MHz, CDCl ₃ , ppm): 8.25 (d, 1H), 8.22 (s, 1H), 7.83 (d, 1H), 7.81 (dd, 1H), 7 .33-7.40 (m, 3H), 7.26-7.33 (m, 4H), 2.35 (s, 3H), 2.14 (s, 3H), 1.95-2.07 (M, 4H), 0.63-0.66 (m, 10H).

[Synthesis Example 4]
(Synthesis of Compound 2)
2-Nitro-9,9-dipropylfluorene 11.82 g (40 mmol) obtained by the method of Synthesis Example 2 and 5.8 g (44 mmol) of aluminum chloride were dissolved in 40 mL of dichloromethane. While cooling the dichloromethane solution in an ice bath, 3.45 g (44 mmol) of acetyl chloride was dropped into the dichloromethane solution at a temperature of 5 ° C. or lower. After dropping, the temperature of the reaction solution was raised to room temperature over 1 hour while stirring the reaction solution, and then the reaction was continued for 3 hours at room temperature.
The obtained reaction solution was dropped into a beaker containing 300 mL of ice water. After the mixture in the beaker was transferred to a separatory funnel, 200 mL of ethyl acetate was added to the separatory funnel, and the product was extracted into an organic layer. After separating the organic layer, the product in the aqueous layer was further extracted with 100 mL of ethyl acetate. The organic layer obtained by the extraction twice was washed with 300 mL of 10% aqueous sodium carbonate solution and then with 300 mL of water. The washed organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off from the organic layer using a rotary evaporator to obtain an oily substance. The oily substance was purified by silica gel column chromatography (developing solvent, ethyl acetate: n-hexane = 1: 1 (mass ratio)) to give a pale yellow solid (2- (2-methylbenzoyl) -7-nitro- 16.11 g (yield 94%) of 9,9-di-n-propylfluorene) was obtained.

After 8.56 g (20 mmol) of the obtained pale yellow solid and 1.5 g (21 mmol) of hydroxylamine hydrochloride were dissolved in 100 mL of ethanol, the ethanol solution was refluxed for 2 hours. Ethanol was distilled off from the reaction solution after reflux, and the residue was washed with water. The washed residue was dissolved in ethyl acetate, and then the ethyl acetate solution was dried over magnesium sulfate. From the dried ethyl acetate solution, the ethyl acetate is removed using a rotary evaporator to obtain an oxime (2-methylphenyl (7-nitro-9,9-di-n-propylfluoren-2-yl) ketone oxime). As a residue. After the obtained oxime body was dissolved in 60 mL of THF, acetyl chloride (3.45 g, 44 mmol) was added to THF, and the reaction was performed with stirring. After the reaction, triethylamine (4.7 g, 46 mmol) was added dropwise to the reaction solution at room temperature. The precipitation of the salt was confirmed with dripping. After stirring the reaction solution to which triethylamine was added for 2 hours, 40 ml of water was added to the reaction solution. Next, the product in the reaction solution was extracted with 40 mL of ethyl acetate. The organic layer was washed twice with 40 mL of water followed by twice with 40 mL of saturated aqueous potassium carbonate solution. The organic layer after washing was dried with magnesium sulfate, and then the solvent was removed from the organic layer using a rotary evaporator to obtain a residue. The residue was purified by silica gel column chromatography (developing solvent, ethyl acetate: n-hexane = 1: 1 (mass ratio)) to obtain compound 2, 6.63 g (16.81 mmol, yield 84%). It was. ¹ H-NMR measurement results of Compound 2 were as follows.
¹ H-NMR (600 MHz, CDCl ₃ , ppm): 8.2 (d, 1H), 8.23 (s, 1H), 7.79-7.83 (m, 4H), 2.48 (s, 3H), 2.27 (s, 3H), 2.06-2.12 (m, 4H), 0.51-0.68 (m, 10H).

[Synthesis Example 5]
(Synthesis of Compound 3)
Compound 3 was prepared in the same manner as in Synthesis Example 3, except that 3.04 g (18.00 mmol) of (2-methylphenyl) acetic acid chloride was changed to 2.89 g (18.00 mmol) of 3-cyclopentylpropionic acid chloride. 4.46 g (10.02 mmol, yield 72%) was obtained. The measurement result of ¹ H-NMR of Compound 3 was as follows.
¹ H-NMR (600 MHz, CDCl ₃ , ppm): 8.06-8.12 (m, 2H), 7.71-7.78 (m, 2H), 7.31-7.40 (m, 3H) ), 2.52 (d, 2H), 2.27 (s, 3H), 1.89-2.19 (m, 5H), 1.48-1.80 (m, 6H), 1.19- 1.26 (m, 2H), 0.61-0.77 (m, 10H).

<Preparation of colorant dispersion>
[Examples 1-30, Comparative Examples 1-8]
The colorant, the dispersant, and the oxime compound shown in Table 1 were mixed and dissolved in the solvent shown in Table 1 to prepare a colorant dispersion having a solid content concentration of 17 to 23% by mass. In addition, the usage-amount of each component is as showing in Table 1. Moreover, the detail of a coloring agent, a dispersing agent, and a solvent is as follows. The mixture 1 of Example 10 is a mixture (mass ratio 1: 1) of the compound 1 (oxime compound) synthesized above and a silane coupling agent having a nitrogen-containing aromatic ring represented by the following formula. Moreover, the mixture 2 of Example 20 is a mixture (mass ratio 1: 1) of the compound 2 (oxime compound) synthesized above and a silane coupling agent having a nitrogen-containing aromatic ring represented by the following formula. Furthermore, the mixture 3 of Example 30 is a mixture (mass ratio 1: 1) of the compound 3 (oxime compound) synthesized above and a silane coupling agent having a nitrogen-containing aromatic ring represented by the following formula.

・着色剤
Ｒ２５４（Ｃ．Ｉ．ピグメントレッド２５４、下記の一番左の式で表されるジケトピロロピロール系顔料）
Ｂ１５：６（Ｃ．Ｉ．ピグメントブルー１５：６、下記の真ん中の式で表されるフタロシアニン系顔料）
Ｇ５８（Ｃ．Ｉ．ピグメントグリーン５８、下記の一番右の式で表されるフタロシアニン系顔料）
Ｐｅｒｙｌｅｎｅ（３，４，９，１０−ペリレンテトラカルボンジアミド：上記式（ｅ−３）において、Ｒ^ｅ７及びＲ^ｅ８が水素原子のもの）

Colorant R254 (CI Pigment Red 254, a diketopyrrolopyrrole pigment represented by the following leftmost formula)
B15: 6 (CI pigment blue 15: 6, phthalocyanine pigment represented by the following middle formula)
G58 (CI Pigment Green 58, phthalocyanine pigment represented by the rightmost formula below)
Perylene (3,4,9,10-perylenetetracarboxylic diamide: in the above formula (e-3), R ^e7 and R ^e8 are hydrogen atoms)

-Dispersant Acrylic resin polymer dispersant (trade name: DisperBYK2001, manufactured by Big Chemie)
・ Solvent: Mixed solvent of 3-methoxybutyl acetate / propylene glycol monomethyl ether acetate = 60/40 (mass ratio)

[Evaluation of viscosity]
Using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.), the viscosity of the colorant dispersion immediately after preparation was measured. In addition, the colorant dispersion was filled in a light-shielding glass container and allowed to stand at 40 ° C. in a sealed state for 7 days, and then the viscosity of the colorant dispersion was measured again using an E-type viscometer. When the difference between the viscosity value immediately after preparation and the viscosity value after standing at 40 ° C. for 7 days is 0.3 mPa · s or less, the dispersion stability of the colorant dispersion is good (◯). When it was determined that the difference was more than 0.3 mPa · s, it was determined that the dispersion stability of the colorant dispersion was poor (x). The results are shown in Table 1.

  As shown in Table 1, in Examples 1, 2, 4-10, 11, 12, 14-20, 21, 22, and 24-30, the addition of compound 1, 2, or 3 allowed Even when the content was reduced, the dispersion stability of the colorant was good. On the other hand, in Comparative Examples 1-8 in which none of Compounds 1 to 3 was used, an amount greater than Examples 1, 2, 4 to 10, 11, 12, 14 to 20, 21, 22, and 24 to 30. When a dispersant is used, the dispersion stability of the colorant is improved, or than Examples 1, 2, 4 to 10, 11, 12, 14 to 20, 21, 22, and 24 to 30 Even when a large amount of dispersant was used, the dispersion stability of the colorant was poor. From the above, it can be seen that the colorant dispersion according to the present invention has good dispersion stability of the colorant even when the content of the dispersant is reduced.

<Preparation of photosensitive resin composition>
[Examples 31 to 66 and Comparative Examples 9 to 19]
20 parts by mass of the photopolymerization initiator described in Table 2 or 3, 30 parts by mass of resin A (solid content 55% by mass, solvent: 3-methoxybutyl acetate), 30 parts by mass of dipentaerythritol hexaacrylate, and Table 2 or 3 100 parts by mass of the colorant dispersion liquid described in (the solid content concentration of each colorant dispersion liquid is 17 to 23% by mass, and the content of the colorant is 15% by mass), and 3-methoxybutyl acetate ( 60% by mass) and a mixed solvent consisting of propylene glycol monomethyl ether acetate (40% by mass) were mixed and then filtered through a membrane filter having a pore size of 5 μm to prepare a photosensitive resin composition. The amount of the mixed solvent was adjusted to adjust the solid content concentration in the photosensitive resin composition to 15% by mass.
Details of “OXE01”, “Compound 1 + OXE01”, and “Compound 2 + OXE01” among the photopolymerization initiators shown in Table 2 or 3 are as follows.
OXE01: Photopolymerization initiator manufactured by BASF (trade name: IRGACURE OXE 01: 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)])
Compound 1 + OXE01: Mixture of Compound 1 and OXE01 (mass ratio 1: 1)
Compound 2 + OXE01: Mixture of Compound 2 and OXE01 (mass ratio 1: 1)

Moreover, what was synthesize | combined according to the following prescription was used for resin A used by preparation of the photosensitive resin composition.
First, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid Was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target value. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by the following structural formula (a-4) of colorless and transparent solid.

  Next, after adding 600 g of 3-methoxybutyl acetate to 307.0 g of the bisphenolfluorene type epoxy acrylate thus obtained and dissolving, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was gradually heated and reacted at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain Resin A. The disappearance of the acid anhydride group was confirmed by IR spectrum. This resin A corresponds to the compound represented by the general formula (a-1).

  About each of the photosensitive resin composition of Examples 31-66 and Comparative Examples 9-19, the evaluation of coloring by post-baking and the evaluation of fine wire adhesion were performed according to the following methods. The results are shown in Tables 2 and 3.

[Coloring evaluation]
About each of the photosensitive resin composition of Examples 31-66 and Comparative Examples 9-19, coloring evaluation was performed in the following procedures.
First, the photosensitive resin composition was spin-coated on a glass substrate (10 cm × 10 cm) and heated at 90 ° C. for 120 seconds to form a 1.0 μm coating film on the surface of the glass substrate. Thereafter, a mirror projection aligner (product name: TME-150 RTO, manufactured by Topcon Corporation) was used, the exposure amount was 20, 50, 100, or 200 mJ / cm ² , the exposure gap was 200 μm, and the coating film was exposed. The exposed film was developed with a 0.04 mass% KOH aqueous solution at 26 ° C. for 30 to 50 seconds, and then post-baked at 230 ° C. for 30 minutes. About the coating film before and behind post-baking, the difference of the transmittance | permeability of 380 nm-780 nm wavelength range was measured as (DELTA) Y using the instantaneous multiphotometry system (MCPD-3000: Otsuka Electronics Co., Ltd. product). The values for ΔY are listed in Tables 2 and 3. It means that it is not colored, so that the absolute value of (DELTA) Y is small.

[Evaluation of fine wire adhesion]
The photosensitive resin compositions of Examples 31 to 66 and Comparative Examples 9 to 19 were applied onto a glass substrate (100 mm × 100 mm) using a spin coater, prebaked at 90 ° C. for 120 seconds, and a film thickness of 1.0 μm. The coating film was formed. Next, a mirror projection aligner (product name: TME-150 RTO, manufactured by Topcon Co., Ltd.) was used, the exposure gap was 50 μm, and the coating film was irradiated with ultraviolet rays through a negative mask on which a 5 μm line pattern was formed. The exposure amount was set in four stages of ²⁰ , 50, 100, and 200 mJ / cm ² . The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26 ° C. for 40 seconds and then post-baked at 230 ° C. for 30 minutes to form a line pattern.

  The formed line pattern was observed with an optical microscope, and fine line adhesion was evaluated. The fine line adhesion was evaluated as “good” when the line pattern was formed without being peeled from the substrate, and “bad” when the line pattern was not formed when peeled from the substrate. The results are shown in Tables 2 and 3.

As can be seen from Tables 2 and 3, in Examples 31 to 66, coloring due to heating during post-baking can be suppressed, and a 5 μm line pattern adhered to the substrate with an exposure amount of 50 mJ / cm ² . . In particular, in Examples 32 to 66, a 5 μm line pattern adhered to the substrate even at a low exposure amount of 20 mJ / cm ² .

In contrast, in Comparative Examples 9, 14, 15, and 17, although coloring due to heating during post-baking could be suppressed, a 5 μm line pattern adhered to the substrate at an exposure amount of 50 mJ / cm ^2. It did not, and was inferior to thin-line adhesiveness compared with Examples 31-66.

Further, in Comparative Examples 10 to 13, 18, and 19, a 5 μm line pattern was adhered to the substrate with an exposure amount of 50 mJ / cm ² , and in particular, in Comparative Examples 10, 18 and 19, it was 20 mJ / cm ^2. Even with a low exposure amount, a 5 μm line pattern adhered to the substrate. However, in Comparative Examples 10 to 13, 18, and 19, coloring due to heating during post-baking could not be suppressed. Although the photosensitive resin composition of Comparative Examples 11 and 13 contains Compound 1 as a photopolymerization initiator, it does not inhibit coloration, so that no interaction occurs between Compound 1 and the colorant. More specifically, considering that the colorant is a pigment made of a nitrogen-containing aromatic ring compound, there is a π-π interaction between the compound 1 and the pigment made of a nitrogen-containing aromatic ring compound. It is thought that it has not occurred.

Furthermore, in Comparative Example 16, coloring due to heating during post-baking could not be suppressed, and with an exposure amount of 50 mJ / cm ² , a 5 μm line pattern did not adhere to the substrate, and Examples 31 to 66 In comparison, the fine wire adhesion was inferior.

Claims (6)

A colorant dispersion containing a colorant, a dispersant, an oxime compound represented by the following formula (1), and a solvent.

(R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, R ² and R ³ are each a chain alkyl group, a cyclic hydrocarbon group, or a heteroaryl group, and R ² and R ³ are ^May combine with each other to form a spiro ring, R ⁴ is a monovalent organic group, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 11 carbon atoms that may have a substituent. Or an aryl group which may have a substituent, and m is 0 or 1.) The colorant dispersion according to claim 1, wherein R ⁴ is a group represented by the following formula (R4-1) or (R4-2).

(In formulas (R4-1) and (R4-2), R ⁶ and R ⁷ are each an organic group, p is an integer of 0 to 4, and R ⁶ and R ⁷ are adjacent positions on the benzene ring. R ⁶ and R ⁷ may be bonded to each other to form a ring, q is an integer of 1 to 8, r is an integer of 1 to 5, and s is 0 to (r + 3). ) And R ⁸ is an alkyl group.)   The colorant dispersion according to claim 1 or 2, wherein m is 1. The colorant dispersion according to claim 1, wherein R ¹ is a hydrogen atom.   The photosensitive resin composition containing base resin, a photoinitiator, and the coloring agent dispersion liquid of any one of Claims 1-4. A dispersion aid comprising an oxime compound represented by the following formula (1).

(R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, R ² and R ³ are each a chain alkyl group, a cyclic hydrocarbon group, or a heteroaryl group, and R ² and R ³ are ^May combine with each other to form a spiro ring, R ⁴ is a monovalent organic group, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 11 carbon atoms that may have a substituent. Or an aryl group which may have a substituent, and m is 0 or 1.)