JP2015052098A - Pigment dispersion, photosensitive resin composition containing the same, and dispersion aid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment dispersion which has good dispersion stability of a pigment even when a content of a dispersant is reduced, and which can give a photosensitive resin composition capable of forming a minute pattern having high adhesiveness even with low exposure luminous energy, and to provide a photosensitive resin composition containing the pigment dispersion, and a dispersion aid.SOLUTION: The pigment dispersion comprises a pigment comprising a nitrogen-containing aromatic ring compound, a dispersant, an oxime ester compound, and a solvent. In the oxime ester compound, a carbon atom included in an oxime group is bonded to an organic group containing an aromatic ring and to an aromatic hydrocarbon ring or an aromatic hetero ring via a carbonyl group. The photosensitive resin composition comprises a base resin, a photopolymerization initiator, and the above pigment dispersion. The dispersion aid comprises the above oxime ester compound.

Description

  The present invention relates to a pigment 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. . In these black matrixes and color filters, a photosensitive resin composition in which black or each color pigment is dispersed is applied to a substrate and dried, and then the obtained 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 pigment dispersion in which a pigment 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 pigment concentration in the photosensitive resin composition that provides the RGB colored layer. However, increasing the concentration of the pigment causes a decrease in the sensitivity of the photosensitive resin composition to light. For example, it becomes difficult to form a pattern having a good shape with a low exposure amount, and the productivity in the exposure process is reduced. It tends to decline.

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

  The present invention has been made in view of such a conventional situation. Even when the content of the dispersant is reduced, the dispersion stability of the pigment is good, and a highly adhesive micropattern is formed even at a low exposure amount. It is an object of the present invention to provide a pigment dispersion capable of providing a possible 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 ester compound to a pigment dispersion containing a pigment comprising a nitrogen-containing aromatic ring compound, and to complete the present invention. It came. Specifically, the present invention provides the following.

  A first aspect of the present invention includes a pigment comprising a nitrogen-containing aromatic ring compound, a dispersant, an oxime ester compound, and a solvent. The oxime ester compound has an aromatic group on a carbon atom contained in the oxime group. It is a pigment dispersion liquid in which an organic group containing a ring and an aromatic hydrocarbon ring or an aromatic heterocyclic ring are bonded via a carbonyl group.

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

  A third aspect of the present invention comprises an oxime ester compound, and the oxime ester compound has an aromatic hydrocarbon ring or a carbon atom contained in the oxime group via an organic group containing an aromatic ring and a carbonyl group. It is a dispersion aid in which an aromatic heterocycle is bonded.

  According to the present invention, even when the content of the dispersant is reduced, the dispersion stability of the pigment is good, and the pigment capable of providing a photosensitive resin composition capable of forming a fine pattern with high adhesion even at a low exposure amount. A dispersion, a photosensitive resin composition containing the dispersion, and a dispersion aid can be provided.

<Pigment dispersion>
The pigment dispersion according to the present invention contains a pigment made of a nitrogen-containing aromatic ring compound, a dispersant, an oxime ester compound, and a solvent. The pigment dispersion according to the present invention does not contain a photopolymerizable compound such as a photopolymerizable monomer or a photopolymerization initiator.

[Pigment made of nitrogen-containing aromatic ring compound]
The pigment dispersion according to the present invention contains a pigment composed of a nitrogen-containing aromatic ring compound. By containing such a pigment, the pigment dispersion according to the present invention is preferably used for forming, for example, a color filter, a paint, a solder resist, and an ink jet ink for a liquid crystal display. The pigments can be used alone or in combination of two or more.

  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 —). Moreover, the phthalimidomethyl group having a substituent represents a structure in which a hydrogen atom in the phthalimidomethyl group is substituted by a substituent, and the 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. As commercial products, product names K0084 and K0086 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, 34, and the like can be preferably used as perylene pigments.

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.

In addition, for the purpose of adjusting the color tone, a pigment made of a nitrogen-containing aromatic ring compound having a color tone of purple, orange, brown, yellow, or the like may be added to the pigment dispersion according to the present invention. For example,
Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, Purple pigments such as 36, 37, 38, 39, 42, 44, 47, 49, 50, Solvent Violet 13, 36,
C. I. Pigment Orange 1, 2, 5, 13, 14, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 40, 43, 46, 48, 49, 51, 61, 62, 63, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and other orange pigments,
C. I. Brown pigments such as CI Pigment Brown 23 and 25,
C. I. And yellow pigments such as CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185.

  The content of the pigment composed of the nitrogen-containing aromatic ring compound is preferably 5 to 95% by mass and more preferably 25 to 90% by mass with respect to the solid content of the pigment dispersion according to the present invention.

[Dispersant]
The pigment dispersion according to the present invention contains a dispersant. When the pigment dispersion contains a dispersant, the pigment is easily dispersed uniformly in the pigment 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 pigment 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 pigment, and 1 to 15 More preferably, it is part by mass. When the content of the dispersant is in the above range, uniform dispersion of the pigment in the pigment 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 ester compound]
The pigment dispersion according to the present invention includes an oxime ester compound in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is bonded to a carbon atom contained in an oxime group via an organic group containing an aromatic ring and a carbonyl group. contains. This oxime ester compound has both a function as a photopolymerization initiator and a function as a dispersion aid. Therefore, when the pigment dispersion containing a pigment made of a nitrogen-containing aromatic ring compound contains the oxime ester compound, the dispersion stability of the pigment tends to be good even if the content of the dispersant is reduced. That is, by using the oxime ester compound, it becomes easy to reduce the content of the dispersant in the pigment dispersion without impairing the dispersion stability of the pigment. As a result, a part of the dispersant is replaced with the oxime ester compound. Since the oxime ester 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 pigment dispersion containing the oxime ester 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 ester compound can be used individually or in combination of 2 or more types.

  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 ester 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 ester 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 ester compound can improve the dispersion stability of a pigment composed of a nitrogen-containing aromatic ring compound.

  The oxime ester compound can be suitably used as a dispersion aid, particularly as a dispersion aid for dispersing a pigment comprising a nitrogen-containing aromatic ring compound.

In the oxime ester compound, the organic group containing an aromatic ring is not particularly limited, and examples thereof include an aryl group which may have a substituent. Examples of the aryl group which may have a substituent include groups exemplified below for R ¹ in the formula (1).

In the oxime ester compound, the aromatic hydrocarbon ring is not particularly limited, and examples thereof include an aryl group which may have a substituent. In the oxime ester compound, the aromatic heterocycle is not particularly limited, and examples thereof include a heteroaryl group which may have a substituent. Examples of the aryl group which may have a substituent and the heteroaryl group which may have a substituent include groups exemplified below for R ² in the formula (1).

  As said oxime ester compound, the oxime ester compound represented by following formula (1) is mentioned, for example.

（式中、Ｒ^１は、置換基を有してもよいアリール基を示し、Ｒ^２は、置換基を有してもよいアリール基、又は置換基を有してもよいヘテロアリール基を示し、Ｒ^３は、水素原子又は炭素数１〜６のアルキル基を示す。）

(In the formula, R ¹ represents an aryl group which may have a substituent, and R ² represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. And R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

In formula (1), R ¹ represents an aryl group which may have a substituent. Examples of the aryl group that may have a substituent include a phenyl group that may have a substituent.

In R ¹ , the substituent that the aryl group or the phenyl group may have is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable substituents that the phenyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, and a substituent. Phenyl group which may have, phenoxy group which may have substituent, phenylthio group which may have substituent, benzoyl group which may have substituent, phenoxy which may have substituent Carbonyl group, optionally substituted benzoyloxy group, optionally substituted phenylalkyl group, optionally substituted naphthyl group, optionally substituted naphthoxy group, substituted A naphthoyl group which may have a group, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent Heterocyclyl group which may have a substituent, Heterocyclylcarbonyl group which may have a substituent, Amino group, Amino group substituted with 1 or 2 organic groups, Morpholin-1-yl group, Piperazine-1- Yl group, halogen atom, nitro group, cyano group and the like.

  When a substituent is an alkyl group, C1-C20 is preferable and C1-C6 is more preferable. When the substituent is an alkyl group, it may be linear or branched. Specific examples when the substituent is an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and 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 the substituent 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 a substituent is an alkoxy group, C1-C20 is preferable and C1-C6 is more preferable. Moreover, when a substituent is an alkoxy group, it may be linear or branched. Specific examples in the case where the substituent is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, 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 the substituent is an alkoxy group, the alkoxy group may include 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 a substituent is a cycloalkyl group or a cycloalkoxy group, C3-C10 is preferable and C3-C6 is more preferable. Specific examples in the case where the substituent 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 in the case where the substituent 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 a substituent is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, C2-C20 is preferable and C2-C7 is more preferable. Specific examples when the substituent 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 the substituent 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 a substituent is an alkoxycarbonyl group, C2-C20 is preferable and C2-C7 is more preferable. Specific examples when the substituent 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, Seo nonyloxycarbonyl group, n- decyl oxycarbonyl group, and the like isodecyl oxycarbonyl group.

  When the substituent is a phenylalkyl group which may have a substituent, the carbon number is preferably 7-20, and more preferably 7-10. Moreover, when a substituent is a naphthyl alkyl group which may have a substituent, C1-C20 is preferable and C-11-C14 is more preferable. Specific examples in the case where the substituent is a phenylalkyl group which may have a substituent include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples in the case where the substituent is an optionally substituted naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2- (α-naphthyl) ethyl group, and 2- (β -Naphthyl) ethyl group.

  When the substituent is a heterocyclyl group which may have a substituent, the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, O, such monocycles, or This is a heterocyclyl group in which a single ring and a benzene ring are condensed. In the case where the heterocyclyl group is a condensed ring, the number is 3. 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 the substituent is an amino group substituted with 1 or 2 organic groups, 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 numbers 2 -20 saturated aliphatic acyl group, phenyl group optionally having substituent, benzoyl group optionally having substituent, phenylalkyl group having 7 to 20 carbon atoms optionally having substituent, substituted Examples thereof include a naphthyl group which may have a group, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group. Specific examples of these suitable organic groups are the same as those exemplified above for the substituent. Specific examples of the amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, and n-butyl. Amino 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, naphthyl Amino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-deca Examples thereof include a noylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

  Examples of the substituent in the case where the phenyl group, naphthyl group, heterocyclyl group, and the like further have a substituent in the above substituent include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; 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; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; Dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl group; piperazin-1-yl group; halogen atom; nitro group; It is. When the phenyl group, naphthyl group, heterocyclyl group and the like contained in the above substituent 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 a phenyl group, a naphthyl group, a heterocyclyl group, and the like have a plurality of substituents, the plurality of substituents may be the same or different.

In formula (1), R ² represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. Examples of the aryl group that may have a substituent include a phenyl group that may have a substituent. Examples of the heteroaryl group which may have a substituent include a carbazolyl group which may have a substituent.

In R ² , the substituent that the aryl group, heteroaryl group, phenyl group, or carbazolyl group may have is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable substituents that the aryl group, heteroaryl group, phenyl group, or carbazolyl group may have on the carbon atom include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, and a saturated aliphatic group. An acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, and a substituent. A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, and a substituent A good naphthyl group, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, and a substituent Good naphthoyloxy group, optionally substituted naphthylalkyl group, optionally substituted heterocyclyl group, optionally substituted heterocyclylcarbonyl group, amino group, 1 or 2 organic groups And an amino group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group and a cyano group substituted with

When R ² is a heteroaryl group or a carbazolyl group, a suitable substituent that the heteroaryl group may have on a heteroatom such as a nitrogen atom, and a preferred case that the carbazolyl group may have on a nitrogen atom Examples of such substituents include alkyl groups, cycloalkyl groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, phenyl groups that may have substituents, benzoyl groups that may have substituents, and substituents. Phenoxycarbonyl group which may have, phenylalkyl group which may have substituent, naphthyl group which may have substituent, naphthoyl group which may have substituent, And a good naphthoxycarbonyl group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, an optionally substituted heterocyclylcarbonyl group, and the like. It is. Among these substituents, an alkyl group is preferable, an alkyl group having 1 to 20 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is still more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent that the aryl group, heteroaryl group, phenyl group, or carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, and a saturated aliphatic acyloxy group. Substituted with a group, an alkoxycarbonyl group, an optionally substituted phenylalkyl group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, and 1 or 2 organic groups The amino group thus prepared is the same as that described for R ¹ .

In the above substituents, the substituent in the case where the phenyl group, naphthyl group, heterocyclyl group and the like further have a substituent is the same as described for R ¹ .

Among R ² , a group represented by the following formula (2) or (3) is preferable, a group represented by the following formula (2) is more preferable, from the viewpoint that the photosensitive resin composition is excellent in sensitivity. A group represented by the formula (2) in which A is S is particularly preferable.

（Ｒ^４は、１価の有機基、アミノ基、ハロゲン原子、ニトロ基、及びシアノ基からなる群より選択される基であり、ＡはＳ又はＯであり、ｎは、０〜４の整数である。）

(R ⁴ is a group selected from the group consisting of a monovalent organic group, amino group, halogen atom, nitro group, and cyano group, A is S or O, and n is an integer of 0-4. .)

（Ｒ^５及びＲ^６は、それぞれ、１価の有機基である。）

(R ⁵ and R ⁶ are each a monovalent organic group.)

When a pattern is formed using the photosensitive resin composition, the pattern is likely to be colored by heating in the post-baking process during pattern formation. However, in the photosensitive resin composition, as a photopolymerization initiator, R ² is a group represented by the above formula (2), and A is a group in which S is a oxime represented by the formula (1) When using an ester compound, the coloring of the pattern by heating can be suppressed.

When R ⁴ in the formula (2) is an organic group, it can be selected from various organic groups as long as the object of the present invention is not impaired. Preferable example of R ⁴ in the formula (2) is an organic group, an alkyl group having 1 to 6 carbon atoms; saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, A benzoyl group substituted by a group selected from the group consisting of a piperazin-1-yl group and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms A dialkylamino group; a morpholin-1-yl group; a piperazin-1-yl group; a halogen; a nitro group; and a cyano group.

In R ⁴ , substituted by a group selected from the group consisting of benzoyl group; naphthoyl group; alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, and phenyl group Benzoyl group; nitro group is preferred, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferred.

In the formula (2), n is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. when n is 1, the binding position of R ⁴ is, relative to the bond to the phenyl group R ⁴ is bonded is bonded to the atom A, it is preferably in the para position.

R ⁵ in Formula (3) can be selected from various organic groups as long as the object of the present invention is not impaired. Preferable examples of R ⁵ include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, Phenyl group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, phenylalkyl having 7 to 20 carbon atoms which may have a substituent Group, an optionally substituted naphthyl group, an optionally substituted naphthoyl group, an optionally substituted naphthoxycarbonyl group, and an optionally substituted carbon number 11 to 20 Naphthylalkyl group, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, and the like.

Among R ⁵ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, an ethyl group is particularly preferred.

R ⁶ in formula (3) is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Specific examples of suitable groups 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 more preferably a phenyl group which may have a substituent, and particularly preferably a 2-methylphenyl group.

In the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R ⁴ , R ⁵ , or R ⁶ further have a substituent, the substituent is an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms. Monoalkylamino having an alkoxy group, 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 Group, 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 contained in R ⁴ , R ⁵ , or R ⁶ further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, 1-4 are preferable. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ⁴ , R ⁵ , or R ⁶ have a plurality of substituents, the plurality of substituents may be the same or different.

In Formula (1), R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ³ is preferably a methyl group or an ethyl group, and more preferably a methyl group.

The oxime ester compound represented by the general formula (1) can be synthesized, for example, according to the following scheme. Specifically, a ketone compound represented by the following general formula (2-1) is added to a nitrite ester (RONO, R represented by the following general formula (2-2) in the presence of hydrochloric acid in the presence of hydrochloric acid. 6) to obtain a ketoxime compound represented by the following general formula (2-3), and then a ketoxime compound represented by the following general formula (2-3) and the following general formula (2). 2-4) is reacted with an acid anhydride ((R ³ CO) ₂ O) or an acid halide represented by the following general formula (2-5) (R ³ COHal, Hal is halogen). Thus, an oxime ester compound represented by the following general formula (2-6) can be obtained. In the following general formulas (2-1), (2-3), (2-4), (2-5), and (2-6), R ¹ , R ² , R ³ , and m are: The same as in the general formula (1).

<Scheme>

Among the oxime ester compounds represented by the general formula (1), the following PI-1 to PI-42 are particularly preferable compounds.

  In the pigment dispersion according to the present invention, the content of the oxime ester compound is not particularly limited as long as the object of the present invention is not impaired. The content of the oxime ester 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 pigment. By setting the content of the oxime ester compound in such a range, the dispersion stability of the pigment tends to be good in the obtained pigment dispersion. In addition, a pigment dispersion in which the content of the oxime ester compound is in 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 pigment dispersion according to the present invention, the total content of the dispersant and the oxime ester compound is preferably 1 to 60 parts by mass, and 1 to 55 parts by mass with respect to 100 parts by mass of the pigment. It is more preferable that it is 1-20 mass parts. When the total content is in the above range, the pigment dispersion and the pigment dispersion can be obtained while ensuring the uniform dispersion of the pigment in the pigment dispersion according to the present invention and the effect of the oxime ester compound. In the photosensitive resin composition, 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 pigment 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, 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 monoalkyl such as monomethyl 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 Ethers: (poly) alkylene glycol monoalkyl ether acetates 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 Kind; di Other ethers such as tylene 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-methoxybutylpropione , 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-butyrate Other esters such as butyl, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methyl Examples include pyrrolidone, N, N-dimethylformamide, amides such as N, N-dimethylacetamide, and the like. 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, the photopolymerizable monomer, the photopolymerization initiator, and the compound represented by the above formula (1) exhibit excellent solubility and are preferable because the dispersibility of the pigment 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 pigment 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 ester compounds]
The pigment dispersion according to the present invention may contain a dispersion aid other than the oxime ester compound as an optional component. The dispersion aid other than the oxime ester 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, A silane coupling agent having a nitrogen-containing aromatic ring is preferred in that a pattern having good water resistance can be formed. 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 pigment dispersion according to the present invention, the content of the dispersion aid other than the oxime ester compound is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass.

[Method for preparing pigment dispersion]
The pigment dispersion according to the present invention is a mixture (dispersion / kneading) of a pigment comprising a nitrogen-containing aromatic ring compound, a dispersant, the oxime ester compound, and a solvent with a stirrer such as a three-roll mill, ball mill, or sand mill. And it can prepare by filtering with filters, such as a 5 micrometer membrane filter, as needed. By preparing (dispersing and kneading) a pigment comprising a nitrogen-containing aromatic ring compound and the oxime ester compound (as a dispersion aid) together with a stirrer in the preparation of the pigment dispersion, It is considered that a π-π interaction occurs between the pigment made of the ring compound and the oxime ester compound, and the effects of the present invention can be obtained.

<Photosensitive resin composition>
The photosensitive resin composition according to the present invention contains at least a base resin, a photopolymerization initiator, and a pigment 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. Further, the oxime ester compound used in the present invention, that is, an organic group containing an aromatic ring and an aromatic hydrocarbon ring or an aromatic heterocyclic ring bonded to a carbon atom contained in the oxime group via a carbonyl group. Oxime ester compounds can also be used as photopolymerization initiators. That is, in the photosensitive resin composition according to the present invention, the oxime ester compound is contained as a dispersion aid (included as a dispersion aid in the pigment dispersion), but is further contained as a photopolymerization initiator. It may be. In this case, it is considered that the oxime ester compound as a photopolymerization initiator does not cause a π-π interaction with a pigment made of a nitrogen-containing aromatic ring compound. The oxime ester compound as the photopolymerization initiator is the same as described above, and the compound represented by the above 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 oxime ester compound as a photopolymerization initiator, the proportion of the oxime ester compound is preferably 1 to 100% by mass with respect to the total amount of the photopolymerization initiator, More preferably, it is -100 mass%, It is further 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.

[Pigment dispersion]
The content of the pigment 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 pigment in the photosensitive resin composition is a solid content of the photosensitive resin composition. The amount of 5 to 70% by mass is preferable with respect to the minute, and the amount of 25 to 60% by mass is more preferable.

  Furthermore, when using the photopolymerizable monomer described later, the content of the pigment dispersion according to the present invention is the sum of the content of the oxime ester compound in the photosensitive resin composition and the base resin and the photopolymerizable monomer. An amount of 0.01 to 2.5 parts by mass is preferable and an amount of 0.01 to 0.5 parts by mass is more preferable with respect to 100 parts by mass. By adjusting the content of the pigment dispersion according to the present invention so that the content of the oxime ester compound in the photosensitive resin composition falls within such a 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 pigment 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 pigment dispersion is prepared by previously mixing a pigment comprising a nitrogen-containing aromatic ring compound, a dispersant, the oxime ester compound, and a solvent. The liquid is mixed with other components such as a base resin. 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 compound 1 and comparative compounds 1 to 4 were used as oxime ester compounds.

<Synthesis of oxime ester compound>
Hereinafter, the synthesis of Compound 1 will be described by Synthesis Example 1.
[Synthesis Example 1]
2- (2-methylphenyl) -1- [4- (phenylsulfanyl) phenyl] ethane-1,2-dione 7.68 g (23.13 mmol) and hydroxylamine hydrochloride 2.93 g (42.16 mmol) Then, 4.15 g (41.01 mmol) of triethylamine was mixed with 64.00 g of ethanol and reacted at 75 ° C. to 80 ° C. for 3 hours. The reaction mixture was evaporated, ethyl acetate was added, washed with saturated brine, dried over anhydrous magnesium sulfate, and evaporated to 2- (2-methylphenyl) 2- (N-hydroxyimino) -1- [4- ( 8.03 g of phenylsulfanyl) phenyl] ethane-1-one were obtained. The obtained 8.03 g of 2- (2-methylphenyl) -2- (N-hydroxyimino) -1- [4- (phenylsulfanyl) phenyl] ethane-1-one was added to acetic anhydride 13 in acetic acid. By acetylation with .33 g (130.57 mmol), 6.25 g of an oxime ester compound represented by the above formula was obtained.

<Preparation of pigment dispersion>
[Examples 1 to 10, Comparative Examples 1 to 10]
The pigment, dispersant, and oxime compound shown in Table 1 were mixed and dissolved in the solvent shown in Table 1 to prepare a pigment 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. Details of the pigment, dispersant, and solvent are as follows. The mixture 1 of Example 10 is a mixture (mass ratio 1: 1) of the compound 1 (oxime ester compound) synthesized above and a silane coupling agent having a nitrogen-containing aromatic ring represented by the following formula.

・顔料
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）

Pigment 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), the viscosity of the pigment dispersion immediately after preparation was measured. The pigment dispersion was filled in a light-shielding glass container and allowed to stand at 40 ° C. for 7 days in a sealed state, and then the viscosity of the pigment 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 pigment dispersion is good (◯). When the difference was more than 0.3 mPa · s, it was determined that the dispersion stability of the pigment dispersion was poor (x). The results are shown in Table 1.

  As shown in Table 1, in Examples 1, 2, and 4 to 10, even when the content of the dispersant was reduced by adding Compound 1, the dispersion stability of the pigment was good. On the other hand, in Comparative Examples 1 to 10 in which Compound 1 was not used, the dispersion stability of the pigment was improved when a larger amount of the dispersant than Examples 1, 2, and 4 to 10 was used, or The dispersion stability of the pigment was poor even when an amount of dispersant greater than Examples 1, 2, and 4-10 was used. From the above, it can be seen that the pigment dispersion according to the present invention has good pigment dispersion stability even when the content of the dispersant is reduced.

<Preparation of photosensitive resin composition>
[Examples 11 to 24 and Comparative Examples 11 to 21]
20 parts by mass of the photopolymerization initiator described in Table 2, 30 parts by mass of resin A (solid content 55% by mass, solvent: 3-methoxybutyl acetate), 30 parts by mass of dipentaerythritol hexaacrylate, and the pigments described in Table 2 100 parts by weight of a dispersion (the solid content concentration of each pigment dispersion is 17 to 23% by weight and the pigment content is 15% by weight), 3-methoxybutyl acetate (60% by weight) and propylene glycol After mixing with a mixed solvent composed of monomethyl ether acetate (40% by mass), the mixture was 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” and “Compound 1 + OXE01” among the photopolymerization initiators shown in Table 2 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)

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 11-24 and Comparative Examples 11-21, 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 Table 2.

[Coloring evaluation]
About each of the photosensitive resin composition of Examples 11-24 and Comparative Examples 11-21, 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 Table 2. 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 11 to 24 and Comparative Examples 11 to 21 were applied on 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 Table 2.

As can be seen from Table 2, in Examples 11 to 24, coloring due to heating during post-baking could 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 12 to 15 and 17 to 24, a 5 μm line pattern adhered to the substrate even at a low exposure amount of 20 mJ / cm ² .

On the other hand, in Comparative Examples 11, 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 was inferior to thin-line adhesiveness compared with Examples 11-24.

Further, in Comparative Examples 12, 13, 20, and 21, a line pattern of 5 μm was adhered to the substrate with an exposure amount of 50 mJ / cm ² , and in particular, in Comparative Examples 12, 20, and 21, 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 12, 13, 20, and 21, coloring due to heating during post-baking could not be suppressed. The photosensitive resin compositions of Comparative Examples 12 and 13 contain Compound 1 as a photopolymerization initiator, but coloring cannot be suppressed. Therefore, between Compound 1 and a pigment comprising a nitrogen-containing aromatic ring compound, π It is considered that −π interaction does not occur.

Further, in Comparative Examples 16, 18, and 19, coloring due to heating during post-baking cannot be suppressed, and a line pattern of 5 μm does not adhere to the substrate at an exposure amount of 50 mJ / cm ² , and the examples Compared with 11-24, it was inferior to thin wire adhesiveness.

Claims (6)

  A pigment comprising a nitrogen-containing aromatic ring compound, a dispersant, an oxime ester compound, and a solvent, wherein the oxime ester compound has an organic group containing an aromatic ring on a carbon atom contained in the oxime group, and a carbonyl group. A pigment dispersion in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is bonded via The pigment dispersion according to claim 1, wherein the oxime ester compound is an oxime ester compound represented by the following formula (1).

(In the formula, R ¹ represents an aryl group which may have a substituent, and R ² represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. And R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) The pigment dispersion according to claim 2, wherein R ² is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent.   The photosensitive resin composition containing base resin, a photoinitiator, and the pigment dispersion liquid of any one of Claim 1 to 3.   The oxime ester compound comprises an oxime group in which an aromatic hydrocarbon ring or an aromatic heterocycle is bonded to a carbon atom contained in an oxime group via an organic group containing an aromatic ring and a carbonyl group. A dispersion aid. The dispersion aid according to claim 5, wherein the oxime ester compound is an oxime ester compound represented by the following formula (1).

(In the formula, R ¹ represents an aryl group which may have a substituent, and R ² represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. And R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)