TW201510108A - Pigment dispersion, photosensitive resin composition containing pigment dispersion, and dispersion aid - Google Patents

Abstract

The present invention provides a pigment dispersion, photosensitive resin composition containing pigment dispersion, and dispersion aid; the pigment dispersion constitutes a photosensitive resin composition; the photosensitive resin composition still has better stability of pigment dispersion even containing reduced amount of dispersion, and further forms highly-adhesive fine patterns under low amount of exposure. The pigment dispersion of the present invention comprises a pigment composed of nitrogen-containing aromatic compounds, a dispersant, an oxime ester compound and a solvent; said oxime ester compound comprises carbon atom in an oxime group which bonds together through containing the organic group and carbonyl group of the aromatic ring, and aromatic hydrocarbon ring or aromatic heterocyclic ring. The photosensitive resin composition of the present invention comprises a base resin, a photopolymerization initiator and the above-described pigment dispersion. The present invention has a dispersion aid composed of the above-described oxime ester compound.

Description

Pigment dispersion, photosensitive resin composition containing the pigment dispersion, and dispersion aid

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

The liquid crystal panel is provided with a black matrix for emphasizing image contrast, or a color filter formed of RGB color layers generally composed of red (R), green (G), and blue (B) colors. Such a black matrix or a color filter is obtained by repeatedly applying a photosensitive resin composition in which a black or a pigment of each color is dispersed onto a substrate, and drying and then exposing and developing the obtained coating film to form a desired one. Formed by the pattern. In order to produce such a photosensitive resin composition, a pigment dispersion liquid in which a pigment is dispersed is used. For example, Patent Document 1 discloses a pigment dispersion liquid containing a pigment, a solvent, a dispersant, and a specific additive having an azo group, a guanamine group, and a carbonyl group.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. 2012-087233

In recent years, technological innovation continues to advance in response to high resolution of liquid crystal panels, and improvement in color development of RGB colored layers is being sought. The coloring property can be improved by increasing the concentration of the pigment in the photosensitive resin composition for forming the RGB colored layer. However, the high sensitivity of the pigment causes the sensitivity of the photosensitive resin composition to light to be lowered. For example, it becomes difficult to form a pattern having a good shape with a low exposure amount, and the productivity in the exposure step is liable to lower.

Further, if the amount of the dispersant in the pigment dispersion liquid can be reduced, in the photosensitive resin composition obtained from the pigment dispersion liquid, the amount of photopolymerization corresponding to the reduction amount can be increased in accordance with the amount of reduction of the dispersant. The amount of the agent or the amount of the photopolymerizable compound such as a photopolymerizable monomer can improve the sensitivity of the photosensitive resin composition to light. For this reason, a technique for achieving good dispersion stability of a pigment even if the content of the dispersant is reduced is sought.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a pigment dispersion liquid, a photosensitive resin composition containing the pigment dispersion liquid, and a dispersion aid which can constitute a photosensitive resin composition. Even if the photosensitive resin composition reduces the content of the dispersant, the dispersion stability of the pigment is good, and a fine pattern having high adhesion can be formed even at a low exposure amount.

As a result of intensive investigation by the inventors of the present invention, it has been found that by adding a specific oxime ester compound to the pigment dispersion liquid, the specific oxime ester compound contains a pigment composed of a nitrogen-containing aromatic ring compound, which can solve the above problems. this invention. In particular, the present invention provides the following techniques.

A first aspect of the present invention is a pigment dispersion containing a pigment, a dispersant, an oxime ester compound and a solvent composed of a nitrogen-containing aromatic ring compound, and the above oxime ester compound is a carbon atom contained on a sulfhydryl group. It is bonded to an aromatic hydrocarbon ring or an aromatic heterocyclic ring via an organic group containing an aromatic ring and a carbonyl group.

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

The third aspect of the present invention is a dispersing aid composed of an oxime ester compound which is a carbon atom contained on a mercapto group, an organic group and a carbonyl group containing an aromatic ring, and an aromatic group. A hydrocarbon ring or an aromatic heterocyclic bond is formed.

According to the present invention, it is possible to provide a pigment dispersion liquid, a photosensitive resin composition containing the pigment dispersion liquid, and a dispersion aid which can constitute a photosensitive resin composition, and the photosensitive resin composition can be dispersed even if it is dispersed. The content of the agent, the dispersion stability of the pigment are still good, and a fine pattern with high adhesion can be formed even with a low exposure amount.

<Pigment dispersion>

The pigment dispersion liquid of the present invention contains a pigment, a dispersant, an oxime ester compound and a solvent composed of a nitrogen-containing aromatic ring compound. In addition, about this The pigment dispersion liquid of the invention does not contain a photopolymerizable compound such as a photopolymerizable monomer or a photopolymerization initiator.

[Pigments composed of nitrogen-containing aromatic ring compounds]

The pigment dispersion of the present invention contains a pigment composed of a nitrogen-containing aromatic ring compound. The pigment dispersion liquid of the present invention is preferably used for the formation of a color filter such as a liquid crystal display, a paint, a solder resist, an ink for inkjet, or the like, by containing such a pigment. These pigments can be used singly or in combination of two or more.

The pigment composed of the nitrogen-containing aromatic ring compound is not particularly limited, and examples thereof include a diketo-pyrrolo-pyrrole pigment, a phthalocyanine pigment, an anthraquinone pigment, and Azo-based pigment, quinophthalone pigment, benzimidazolone pigment, isoindolinone pigment, two The pigment, the indanthrene pigment, and the like are preferably a diketopyrrolopyrrole pigment, a phthalocyanine pigment, and/or an anthraquinone pigment.

The diketopyrrolopyrrole pigment is not particularly limited, and examples thereof include compounds represented by the following formula (b-1).

In the formula (b-1), A ³ and A ⁴ each independently represent a halogen atom, a methyl group, an ethyl group, a tertiary butyl group, a phenyl group, an N,N-dimethylamino group, a trifluoromethyl group, or a cyano group. , k and k' each independently represent an integer of 0 to 5. When k and k' are each an integer of 2 or more, most of A ³ and A ⁴ may be the same or different.

In the formula (b-1), k and k' are each independently an integer of 0 to 5. Among them, from the point of achieving a high contrast and easily adjusting the red color suitable for a color filter or the like, k and k' are preferably independent integers of 0 to 3, and k and k' are preferably independent of each other. Or an integer of 1.

As the diketopyrrolopyrrole pigment, among the characteristics of a color filter capable of forming high brightness and high contrast, CI Pigment Red 254, CI Pigment Red 255, CI Pigment are preferred. Red 264, CI Pigment Red 270, CI Pigment Red 272, CI Pigment Orange 71, and CI Pigment Orange 73 are more preferably CI Pigment Red 254 or CI Pigment Red 255 from the characteristics of hue and color strength. The diketopyrrolopyrrole pigments can be used alone or in combination of two or more.

The average primary particle diameter 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, more preferably in the range of 10 to 30 nm. By the average primary particle diameter of the pigment in the above range, for example, the color filter can be made highly contrasted and of high quality. Further, the average particle diameter of the above pigment can be determined by a method of directly measuring the size of primary particles from an electron micrograph. Specifically, the minor axis diameter and the major axis diameter of each primary particle are measured, and the average is taken as the particle diameter of the particle. its In the case of 100 or more particles, the volume (mass) of each particle is obtained by a rectangular parallelepiped which approximates the obtained particle diameter, and the volume average particle diameter is determined and used as an average particle diameter. In addition, the same result can be obtained by using either of a transmission type (TEM) and 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. Further, a commercially available diketopyrrolopyrrole pigment can also be used.

The phthalocyanine pigment is not particularly limited, and examples thereof include compounds represented by the following formula (b-2).

[wherein, X ₁ to X ₄ each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, and a heterocyclic ring which may have a substituent The alkoxy group which may have a substituent, the aryloxy group which may have a substituent, the alkylthio group which may have a substituent, or the arylthio group which may have a substituent. Y ₁ to Y ₄ each independently represent a halogen atom, a nitro group, a benzyl quinone imine methyl group which may have a substituent, or an amine sulfonyl group which may have a substituent. 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 represent an integer of 0 to 4, and m1+n1, m2+n2, m3+n3, and m4+n4 are each an integer of 0 to 4, which may be The same can be different. 〕

In the general formula (b-2), X ₁ to X ₄ may be the same or different, and specific examples thereof include an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substitution. a cycloalkyl group, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or may have The arylthio group of the substituent. When the above X ₁ to X ₄ have a substituent, the substituents may be the same or different, and specific examples thereof include a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, and a characteristic group such as an amine group, a hydroxyl group or a nitro group. Examples thereof include an alkyl group, an aryl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group and the like. Moreover, such substituents may also be a plurality.

Examples of the "alkyl group" which may have a substituent alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a neopentyl group, and a n-hexyl group. a straight-chain or branched alkyl group such as an n-octyl group, a stearyl group or a 2-ethylhexyl group; and the "alkyl group having a substituent" may, for example, be a trichloromethyl group, a trifluoromethyl group or a 2,2 group. 2-Trifluoroethyl, 2,2-dibromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl Base, benzyl, 4-methylbenzyl, 4-triisopropyl benzyl, 4-methoxybenzyl, 4-nitrobenzyl, 2,4-dichlorobenzyl, and the like.

Examples of the "aryl group" which may have an aryl group having a substituent include a phenyl group, a naphthyl group, an anthracenyl group and the like; and the "aryl group having a substituent" may be exemplified Methylphenyl, p-bromophenyl, p-nitrophenyl, p-methoxyphenyl, 2,4-dichlorophenyl, pentafluorophenyl, 2-aminophenyl, 2-methyl-4 -Chlorophenyl, 4-hydroxy-1-naphthyl, 6-methyl-2-naphthyl, 4,5,8-trichloro-2-naphthyl, anthracenyl, 2-aminoindenyl, etc. .

Examples of the "cycloalkyl group" which may be a cycloalkyl group having a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like; and the "cycloalkyl group having a substituent" may, for example, be 2,5- Dimethylcyclopentyl, 4-tributylcyclohexyl and the like.

Examples of the "heterocyclic group" which may have a heterocyclic group of a substituent include a pyridyl group, a pyrazolyl group, a piperidinyl group, a piperidyl group, a morpholinyl group, an acridinyl group, and the like; Examples of the heterocyclic group of the group include a 3-methylpyridyl group, an N-methylpiperidinyl group, and an N-methylpyrrolyl group.

Examples of the "alkoxy group" which may have a substituent alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, and a tertiary butyl group. Straight or branched chain such as oxy, neopentyloxy, 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy, 2-ethylhexyloxy Alkoxy; as a "alkoxy group having a substituent", a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, 2,2,3,3- Tetrafluoropropoxy, 2,2-bistrifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, benzyloxy, and the like.

Examples of the "aryloxy group" which may have an aryloxy group having a substituent include a phenoxy group, a naphthyloxy group, a decyloxy group, and the like; and the "aryloxy group having a substituent" includes a p-methyl group. Phenoxy, p-nitrophenoxy, p-methoxyphenoxy, 2,4-dichlorophenoxy, pentafluorophenoxy, 2-methyl-4-chlorophenoxy and the like.

As the "alkylthio group" which may have a substituent alkylthio group, Methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, octylthio, sulfonylthio, dodecylthio, octadecylthio, etc.; Examples of the alkylthio group include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group and the like.

Examples of the "arylthio group" which may have an arylthio group having a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-fluorenylthio group, and the like; Examples of the sulfur group include a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, and a 2-hydroxyphenylthio group.

Next, specific examples of Y ₁ to Y ₄ include a halogen atom, a nitro group, and a benzoquinone imine methyl group (C ₆ H ₄ (CO) ₂ N-CH ₂ -) which may have a substituent. Aminesulfonyl (H ₂ NSO ₂ -). Further, the benzyl quinone imine methyl group having a substituent means a structure in which a hydrogen atom in a benzyl quinone imine methyl group is substituted with a substituent, and the amine sulfonyl group having a substituent means an amine. A structure in which a hydrogen atom in a sulfonyl group is substituted with a substituent. Desirable Y ₁ to Y ₄ are a halogen atom and an amine sulfonyl group. A phthalocyanine compound in which m1 to m4 are 0 (in other words, there is no Y ₁ to Y ₄ ) can be suitably used. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The "substituent" which may also have a substituent of a xylylenediamine methyl group and an aminesulfonyl group which may have a substituent is synonymous with a substituent of X ₁ to X ₄ .

As the phthalocyanine pigment, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Green 58, CI Pigment Blue 16, CI Pigment Blue 75, and CI Pigment Blue 15 (including from 15: 1 to 15:6, etc.), more preferably CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Blue 15:1 to 15:6.酞Cyanine pigments can be used alone or in combination 2 More than one kind to use.

The phthalocyanine pigment used in the present invention can be produced by a known method. Further, commercially available phthalocyanine pigments can also be used.

Examples of the fluorene-based pigments include an anthraquinone pigment represented by the following formula (e-1), an anthracene pigment represented by the following formula (e-2), and an anthracene pigment represented by the following formula (e-3). Among the commercially available products, product names K0084 and K0086 or pigment blacks 21, 30, 31, 32, 33, and 34 manufactured by BASF Corporation can be preferably used as the fluorene-based pigment.

In the 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 an ethylidene group. .

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

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

For example, a compound represented by the above formula (e-1), a compound represented by the formula (e-2), and a compound represented by the formula (e-3) can be used, for example, in Japanese Patent Laid-Open No. 62-1753, The method described in Japanese Patent Publication No. 63-26784 and the like is synthesized. That is, hydrazine-3,5,9,10-tetracarboxylic acid or a dianhydride thereof and an amine are used as a raw material, and a heating reaction is carried out in water or an organic solvent. Then, the object obtained can be obtained by reprecipitating the obtained crude product in sulfuric acid or by recrystallization in water, an organic solvent or a mixed solvent of these.

In order to disperse the lanthanoid pigment well, the average particle diameter of the lanthanoid pigment is preferably from 10 to 1,000 nm.

Further, in the pigment dispersion liquid of the present invention, a pigment composed of a nitrogen-containing aromatic ring compound having a hue of purple, orange, brown or yellow may be added for the purpose of adjusting the color tone. 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, 36, 37, 38, 39, 42, 44, 47, 49, 50, Solvent Violet 13, 36 and other purple pigments; CI 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; CI pigment brown 23, 25 and other brown pigments; CI pigment yellow 83 Yellow pigments such as 117, 129, 138, 139, 150, 154, 155, 180, 185.

The content of the pigment composed of the nitrogen-containing aromatic ring compound is preferably from 5 to 95% by mass, more preferably from 25 to 90% by mass, based on the solid content of the pigment dispersion liquid of the present invention.

〔Dispersant〕

The pigment dispersion of the present invention contains a dispersant. When the pigment dispersion liquid contains a dispersant, the pigment is easily dispersed uniformly in the pigment dispersion liquid. The dispersing agent may be used singly or in combination of two or more.

As a dispersing agent, a polyethyleneimine-based polymer dispersing agent, a urethane resin-based polymer dispersing agent, and an acrylic resin-based polymer dispersing agent are preferably used.

The content of the dispersant in the pigment dispersion liquid of the present invention is preferably from 1 to 50 parts by mass, more preferably from 1 to 20 parts by mass, even more preferably from 1 to 15 parts by mass, per 100 parts by mass of the pigment. If the content of the dispersant is in the above range, the pigment in the pigment dispersion of the present invention becomes more easily and uniformly dispersed. In addition, the lower the upper limit, the balance of each component in the photosensitive resin composition described later is likely to be good, and the other components in the photosensitive resin composition can be blended. The combination increases relatively, so that other characteristics such as sensitivity are easily improved. The effect on the sensitivity characteristics, particularly when a blue pigment that absorbs the photosensitive wavelength is used is good.

[肟 ester compound]

The pigment dispersion liquid of the present invention contains an oxime ester compound which is bonded to an aromatic hydrocarbon ring or an aromatic heterocyclic ring via a carbon atom contained in the fluorenyl group via an organic group containing a aromatic ring and a carbonyl group. This oxime ester compound has both the function as a photopolymerization initiator and the function as a dispersing aid. Therefore, when the pigment dispersion liquid containing the pigment composed of the nitrogen-containing aromatic ring compound contains the above-described oxime ester compound, it is easy to make the dispersion stability of the pigment good even if the content of the dispersant is reduced. That is, since the above oxime ester compound is used, it becomes easy to reduce the content of the dispersing agent in the pigment dispersion liquid without impairing the dispersion stability of the pigment. As a result, a part of the dispersing agent is replaced with the above oxime ester compound. The above oxime ester compound has a function as a photopolymerization initiator, and the above substitution corresponds to a reduction in the dispersant content and an increase in the photopolymerization initiator content. Therefore, the content of the photopolymerization initiator can be increased from the photosensitive resin composition obtained from the pigment dispersion containing the above oxime ester compound, and the photosensitive resin composition can easily form a high adhesion with a low exposure amount. Tiny pattern. These oxime ester compounds can be used individually or in combination of 2 or more types.

Among the pigments composed of the nitrogen-containing aromatic ring compound, the π-electron system is affected by the nitrogen atoms contained in the molecule, and is in an unstable state as compared with the case where the nitrogen atom is not contained. Therefore, the pigment composed of the nitrogen-containing aromatic ring compound is less likely to be excellent in dispersion stability. The pigment dispersion of the present invention The above oxime ester compound has a sulfhydryl group and a carbonyl group, and an aromatic ring is bonded to the group to form a stable π-electron system. It is presumed that a π-π interaction occurs between the above oxime ester compound and a pigment composed of a nitrogen-containing aromatic ring compound, and the molecules are stacked on each other to stabilize the π-electron system of the above pigment. As a result, it is considered that the above oxime ester compound can improve the dispersion stability of the pigment composed of the nitrogen-containing aromatic ring compound.

The above oxime ester compound can be suitably used as a dispersing aid, and particularly as a dispersing aid for dispersing a pigment composed of a nitrogen-containing aromatic ring compound.

The oxime ester compound is not particularly limited as the organic group containing an aromatic ring, and examples thereof include an aryl group which may have a substituent. The aryl group which may have a substituent may, for example, be a group exemplified for R ¹ in the formula (1).

The oxime ester compound is not particularly limited as the aromatic hydrocarbon ring, and examples thereof include an aryl group which may have a substituent. Further, the oxime ester compound is not particularly limited as the aromatic heterocyclic ring, 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 the groups exemplified for R ² in the formula (1).

The oxime ester compound is, for example, an oxime ester compound represented by the following formula (1).

(wherein R ¹ represents an aryl group which may have a substituent, 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 a carbon number of 1 to 6 Alkyl.)

In the formula (1), R ¹ represents an aryl group which may have a substituent. The aryl group which may have a substituent may, for example, be a phenyl group which may have a substituent.

In R ¹ , the aryl group or the phenyl group may have a substituent, and the scope of the object of the present invention is not particularly limited. Examples of suitable substituents which the phenyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, a saturated aliphatic decyloxy group, an alkoxycarbonyl group, and the like. a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a benzamyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzyl methoxy group having a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, and a naphthyl group which may have a substituent A mercapto group, a naphthyloxycarbonyl group having a substituent, a naphthylmethoxy group which may have a substituent, a naphthyl group which may have a substituent, a heterocyclic group which may have a substituent, or a substituent a heterocyclic carbonyl group, an amine group, an amine group substituted with 1 or 2 organic groups, a phenanthroline-1-yl group, a piperidine a -1- group, a halogen atom, a nitro group, a cyano group, and the like.

When the substituent is an alkyl group, it preferably has a carbon number of 1 to 20, more preferably a carbon number of 1. ~6. When the substituent is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where the substituent is an alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, and a n-pentyl group. Isoamyl, secondary pentyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, secondary octyl, tertiary octyl, n-decyl, isodecyl, n-decyl , and different bases, etc. Further, when the substituent is an alkyl group, the alkyl group may have 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, and a propoxy group B. Oxyethyl, methoxypropyl and the like.

When the substituent is an alkoxy group, it preferably has a carbon number of from 1 to 20, more preferably a carbon number of from 1 to 6. Further, when the substituent is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where the substituent is an alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a secondary butoxy group, and the like. Butoxy, n-pentyloxy, isopentyloxy, secondary pentyloxy, tertiary pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, secondary octyloxy a group, a tertiary octyloxy group, a n-decyloxy group, an isodecyloxy group, a n-decyloxy group, an isodecyloxy group, and the like. Further, when the substituent is an alkoxy group, the alkoxy group may have 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, and an ethoxyethoxyethoxy group. , propoxyethoxyethoxy, and methoxypropoxy.

When the substituent is a cycloalkyl group or a cycloalkoxy group, it preferably has a carbon number of 3 to 10, more preferably a carbon number of 3 to 6. Specific examples of 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 of the case where the substituent is a cycloalkoxy group include a cyclopropoxy group and a cyclobutene. An oxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, and the like.

When the substituent is a saturated aliphatic fluorenyl group or a saturated aliphatic fluorenyloxy group, it preferably has a carbon number of 2 to 20, more preferably a carbon number of 2 to 7. Specific examples of the case where the substituent is a saturated aliphatic fluorenyl group include an ethyl fluorenyl group, a propyl fluorenyl group, a n-butyl fluorenyl group, a 2-methyl propyl fluorenyl group, a n-pentamethylene group, and a 2,2-dimethyl propyl hydrazine group. Base, positive hexyl group, n-heptyl sulfhydryl group, n-octyl sulfhydryl group, n-decyl group, n-decyl group, positive eleventh fluorenyl group, positive zirconium group, positive thirteenth fluorenyl group, positive fourteenth fluorenyl group, positive ten Wuyiji, and Zhengliujiji, etc. Specific examples of the case where the substituent is a saturated aliphatic oxime group include an ethoxycarbonyl group, a propenyloxy group, a n-butenyloxy group, a 2-methylpropenyloxy group, a n-pentamoxy group, and 2 ,2-dimethylpropoxycarbonyl, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy, n-decyloxy, n-xyl Alkoxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecanoyloxy and the like.

When the substituent is an alkoxycarbonyl group, it preferably has a carbon number of 2 to 20, more preferably a carbon number of 2 to 7. Specific examples of the case where the substituent is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, an isobutoxycarbonyl group, a secondary butoxycarbonyl group, and the like. Butyroxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, secondary pentyloxycarbonyl, tertiary pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, secondary Octyloxycarbonyl, tertiary octyloxycarbonyl, n-nonyloxycarbonyl, isodecyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl, and the like.

When the substituent is a phenylalkyl group which may have a substituent, the carbon number is preferably from 7 to 20, more preferably from 7 to 10. Further, when the substituent is a naphthyl group which may have a substituent, the number of carbon atoms is preferably from 11 to 20, more preferably from 11 to 14. Specific examples of 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 of the case where the substituent is a naphthyl group which may have a substituent include α -naphthylmethyl, β -naphthylmethyl, 2-( α -naphthyl)ethyl, and 2-( β- Naphthyl)ethyl.

When the substituent is a heterocyclic group which may have a substituent, the above heterocyclic group is a single ring of 5 or 6 members containing one or more of N, S, and O, or a related single ring or a related single ring and a heterocyclic group in which a benzene ring is condensed. When the above heterocyclic group is a condensed ring, it is provided in the number of rings to 3. Examples of the heterocyclic ring constituting the related heterocyclic group include furan, thiophene, and pyrrole. Oxazole Oxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridyl (pyrazine), pyrimidine, pyrene (pyridazine), benzofuran, benzothiophene, hydrazine, isoindole, hydrazine (indolizine), benzimidazole, benzotriazole, benzo Azole, benzothiazole, carbazole, anthracene, quinoline, isoquinoline, quinazoline, anthracene (phthalazine), Cinnoline, and quinine Quinoxaline and the like.

When the substituent is an amine group substituted with 1 or 2 organic groups, a suitable example of the organic group is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a carbon number of 2 a saturated aliphatic fluorenyl group of ～20, a phenyl group which may have a substituent, a benzyl fluorenyl group which may have a substituent, a phenylalkyl group having a carbon number of 7 to 20 which may have a substituent, or a substituent The naphthyl group may be a naphthylmethyl group which may have a substituent, a naphthyl group having a carbon number of 11 to 20 which may have a substituent, and a heterocyclic group. Specific examples of such suitable organic groups are the same as those exemplified above for the substituents. Specific examples of the amine group substituted with one or two organic groups include a methylamino group, an ethylamino group, a diethylamino group, a n-propylamino group, a di-n-propylamino group, an isopropylamine group, and a n-butylamino group. , bis-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-nonylamino, anilino, naphthylamino, acetoamine, C Amidino, n-butylamino, n-pentamethylene, n-hexylamine, n-heptylamino, n-octylamine, n-nonylamine, benzamidine, alpha -naphthoquinone Amine group, and β -naphthylamino group and the like.

In the above substituent, examples of the substituent in the case where the phenyl group, the naphthyl group, and the heterocyclic group further have a substituent include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. a saturated aliphatic fluorenyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic fluorenyl group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzamidine group; Base; to select an alkyl group having a free carbon number of 1 to 6, a phenanthroline-1-yl group, a piperidine a benzyl group substituted with a group of a group of -1- groups and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamine having an alkyl group having 1 to 6 carbon atoms; Base; phenanthroline-1-yl; -1-yl; halogen atom; nitro; cyano group. When the phenyl group, the naphthyl group, the heterocyclic group or the like contained in the above substituent further has a substituent, the number of the substituents is not limited, and is preferably from 1 to 4, without departing from the scope of the object of the present invention. When a phenyl group, a naphthyl group, a heterocyclic group or the like has a plurality of substituents, most of the substituents may be the same or different.

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

The substituent which the aryl group, the heteroaryl group, the phenyl group, or the carbazolyl group may have in R ² is not particularly limited insofar as it does not impair the object of the present invention. Examples of the aryl group, heteroaryl group, phenyl group or carbazolyl group which may have a suitable substituent on the carbon atom include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, and a saturated group. An aliphatic fluorenyl group, a saturated aliphatic decyloxy 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, or a substituent a benzhydryl group, a phenoxycarbonyl group which may have a substituent, a benzylideneoxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, or may have a naphthyloxy group of a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylmethoxy group which may have a substituent, a naphthyl group which may have a substituent, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amine group, an amine group substituted with 1 or 2 organic groups, a phenanthroline-1-yl group, a piperidine a -1- group, a halogen atom, a nitro group, a cyano group, and the like.

When R ² is a heteroaryl group or a carbazolyl group, the heteroaryl group may have a suitable substituent at a hetero atom such as a nitrogen atom, and the carbazolyl group may have a suitable substituent on the nitrogen atom. Examples thereof include an alkyl group, a cycloalkyl group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a phenyl group which may have a substituent, a benzamyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having a substituent, a naphthyl group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthyl group which may have a substituent, A heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, and the like. Among these substituents, an alkyl group is preferred, an alkyl group having 1 to 20 carbon atoms is more preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred.

Specific examples of the substituent which the aryl group, heteroaryl group, phenyl group, or carbazolyl group may have, regarding an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, a saturated aliphatic fluorenyl group, and a saturated fat a cerium oxy group, an alkoxycarbonyl group, a phenylalkyl group which may have a substituent, a naphthyl group which may also have a substituent, a heterocyclic group which may have a substituent, and an amine substituted with 1 or 2 organic groups The base is the same as that described for R ¹ .

Among the above substituents, the substituents when the phenyl group, the naphthyl group, and the heterocyclic group further have a substituent are the same as those described for R ¹ .

Among the R ² , the photosensitive resin composition is excellent in sensitivity, and is preferably a group represented by the following formula (2) or (3), more preferably a group represented by the following formula (2), and the following The formula (2) represents a group, and particularly preferably A is a group of S.

(R ⁴ is a group in which a monovalent organic group, an amine group, a halogen atom, a nitro group, and a cyano group are selected, and A is S or O, and n is an integer of 0 to 4.)

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

When a pattern is formed using a photosensitive resin composition, coloring of the pattern is apt to occur due to heating in a post-bake step at the time of pattern formation. However, in the photosensitive resin composition, an oxime ester compound represented by the formula (1) wherein R ² is a group represented by the above formula (2) and A is a group of S as a photopolymerization initiator is used. In this case, it is possible to suppress the coloration of the pattern caused by the heating.

When R ⁴ in the formula (2) is an organic group, various organic groups can be selected without departing from the object of the present invention. Examples of suitable examples of the formula (2) in which R ⁴ is an organic group include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; and a saturated aliphatic fluorenyl group having 2 to 7 carbon atoms. ; alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic methoxy group having 2 to 7 carbon atoms; phenyl; naphthyl group; benzamidine group; naphthylmethyl group; Base, phenanthroline-1-yl, piperazine a benzyl group substituted with a group of a group of -1- groups and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamine having an alkyl group having 1 to 6 carbon atoms; Base; phenanthroline-1-yl; -1-yl; halogen; nitro; cyano.

Among R ⁴ , preferred is: benzylidene group; naphthylmethyl group; to select an alkyl group having a free carbon number of 1 to 6, a phenanthroline-1-yl group, a piperidine a benzyl group substituted with a group of a group of a group of -1- groups and a phenyl group; a nitro group. More preferably: benzylidene; naphthylmethyl; 2-methylphenylcarbonyl; 4-(piperider -1-yl)phenylcarbonyl; 4-(phenyl)phenylcarbonyl.

Further, in the formula (2), n is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, particularly preferably 0 or 1. n is 1, the bonding position of R ^4, with respect to the atom bonded to the phenyl group and A atoms of R ⁴ are bonded, preferably para.

R ⁵ in the formula (3) can be selected from various organic groups without departing from the object of the present invention. Suitable 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 fluorenyl group having 2 to 20 carbon atoms, and an alkoxy group having 2 to 20 carbon atoms. a carbonyl group, a phenyl group which may have a substituent, a benzylidene group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having a substituent of 7 to 20 carbon atoms, or a naphthyl group having a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthyl group having a carbon number of 11 to 20 which may have a substituent, or a substituent A heterocyclic group, a heterocyclic carbonyl group which may have a substituent, and the like.

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

R ⁶ in the formula (3) is not particularly limited insofar as it does not impair the object of the present invention, and various organic groups can be selected. Specific examples of a suitable group of 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 heterocyclic ring which may have a substituent. base. As R ⁶ , among these, a phenyl group which may have a substituent is preferable, and a 2-methylphenyl group is particularly preferable.

Examples of the substituent in the case where the phenyl group, the naphthyl group, and the heterocyclic group contained in R ⁴ , R ⁵ or R ⁶ further have a substituent include an alkyl group having 1 to 6 carbon atoms and a carbon number of 1 to 6 Alkoxy group, saturated aliphatic fluorenyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated aliphatic decyloxy group having 2 to 7 carbon atoms, alkyl group having 1 to 6 carbon atoms Monoalkylamino group, dialkylamino group having an alkyl group having 1 to 6 carbon atoms, phenanthroline-1-yl group, and piperazine -1-yl, halogen, nitro, and cyano. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ⁴ , R ⁵ or R ⁶ further have a substituent, the number of the substituents is not limited, and is preferably 1 insofar as the object of the present invention is not impaired. ~4. When a phenyl group, a naphthyl group, and a heterocyclic group contained in R ⁴ , R ⁵ or R ⁶ have a plurality of substituents, most of the substituents may be the same or different.

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

The oxime ester compound represented by the formula (1) can be synthesized, for example, according to the following scheme. Specifically, a ketone compound represented by the following formula (2-1) is present in the presence of citric acid and a nitrite represented by the following formula (2-2) (RONO, R is a carbon number of 1 to 6) The alkyl group is subjected to a reaction to obtain a ketoxime compound represented by the following formula (2-3), followed by a ketone oxime compound represented by the following formula (2-3) and a formula (2-4) The acid anhydride ((R ³ CO) ₂ O) or the acid halide (R ³ COHal, Hal is a halogen) represented by the following formula (2-5) can be obtained by the following formula (2) -6) represents an oxime ester compound. Further, in the following general formulae (2-1), (2-3), (2-4), (2-5), and (2-6), R ¹ , R ² , R ³ , and m are It is the same as the general formula (1).

Among the compounds particularly suitable for the oxime ester compound represented by the formula (1), the following PI-1 to PI-42 are mentioned.

In the pigment dispersion liquid of the present invention, the content of the above oxime ester compound is not particularly limited insofar as it does not impair the object of the present invention. The content of the above-mentioned oxime ester compound is preferably from 1 to 50 parts by mass, more preferably from 1 to 10 parts by mass, per 100 parts by mass of the pigment. By setting the content of the above oxime ester compound in such a range, the dispersion stability of the pigment in the obtained pigment dispersion liquid tends to be good. Further, the pigment dispersion liquid having a content of the above oxime ester compound in the above range can be suitably used for preparation to form a high exposure amount with a low exposure amount. A photosensitive resin composition having a fine pattern of adhesion.

Further, in the pigment dispersion liquid of the present invention, the total content of the dispersant and the oxime ester compound is preferably 1 to 60 parts by mass, more preferably 1 to 55 parts by mass, even more preferably 100 parts by mass of the pigment. 1 to 20 parts by mass. When the total content is within the above range, not only the pigment in the pigment dispersion of the present invention is uniformly dispersed or the effect of the above-described oxime ester compound, but also the above pigment dispersion and the photosensitive resin composition obtained from the pigment dispersion are obtained. In this case, the balance of each component tends to be good. Further, since the upper limit is smaller, the blending amount of other components in the photosensitive resin composition can be relatively increased, and thus other characteristics such as sensitivity can be easily improved.

[solvent]

Examples of the solvent in the pigment dispersion liquid of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, and 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 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, etc. Alkyl glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate (poly)alkylene glycol monoalkyl ether acetates such as ester, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, two Other ethers such as ethylene glycol diethyl ether and tetrahydrofuran; methyl ethyl ketone, a ketone such as cyclohexanone, 2-heptanone or 3-heptanone; an alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; 2-hydroxy-2-methylpropane Ethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate , ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate , ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-butyrate Ester, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate And other esters; aromatic hydrocarbons such as toluene and xylene; decylamines such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide Classes, etc. The solvent can be used singly or in combination of two or more.

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 ether And cyclohexanone and 3-methoxybutyl acetate can be displayed for the alkali-soluble resin, photopolymerizable monomer, and photopolymerization initiator described later, and for the compound represented by the above formula (1) It is excellent in solubility and good in dispersibility of the above pigment, and it is particularly preferable to use propylene glycol monomethyl ether acetate or 3-methoxybutyl acetate.

The solid content concentration of the pigment dispersion liquid of the present invention is preferably from 1 to 50% by mass, and more preferably from 5 to 30% by mass.

[Dispersing aids other than oxime ester compounds]

The pigment dispersion liquid of the present invention may contain an optional component other than the above-described oxime ester compound as an optional component. The dispersing aid other than the oxime ester compound is preferably a dispersing aid having a nitrogen-containing aromatic ring in terms of stacking property. For example, a photosensitive resin composition described later can be used to form adhesion to a substrate and water resistance. In terms of a good pattern, a decane coupling agent having a nitrogen-containing aromatic ring is preferred. As the decane coupling agent having a nitrogen-containing aromatic ring, specifically, it is preferably represented by the following formula (11).

R ¹¹ _p R ¹² _(3-p) Si-R ¹³ -NH-C(O)-YR ¹⁴ -X‧‧‧(11) (In the formula (11), R ¹¹ is an alkoxy group, and R ¹² is an alkane a group, p is an integer of 1 to 3, R ¹³ is an alkylene group, Y is -NH-, -O-, or -S-, R ¹⁴ is a single bond or an alkyl group, and X may have a substituent. Further, it may be a monocyclic ring or a polycyclic nitrogen-containing heteroaryl group, and the ring bonded to -YR ¹⁴ - in X is a nitrogen-containing 6-membered aromatic ring, -YR ¹⁴ - and the aforementioned nitrogen-containing 6-member aromatic ring. Carbon atom bonding.)

In the formula (11), R ¹¹ is an alkoxy group. With respect to R ¹¹ , the number of carbon atoms of the alkoxy group is preferably from 1 to 6, more preferably from 1 to 4, and particularly preferably from 1 or 2 from the viewpoint of reactivity of the decane coupling agent. Preferred examples of R ¹¹ include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a secondary butoxy group, and a tertiary butoxide. Base, n-pentyloxy, and n-hexyloxy. Among these alkoxy groups, a methoxy group and an ethoxy group are preferred.

The alkoxy group, that is, the sterol group formed by hydrolysis of R ¹¹ reacts with the surface of the substrate or the like, and the adhesion of the pattern formed using the photosensitive resin composition described later to the surface of the substrate is improved. Therefore, p is preferably 3 from the viewpoint of easily improving the adhesion of the pattern to the surface of the substrate.

In the formula (11), R ¹² is an alkyl group. With respect to R ¹² , the number of carbon atoms of the alkyl group is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 1 or 2 from the viewpoint of reactivity of the decane coupling agent. Preferred examples of R ¹² include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a n-pentyl group, and a n-hexyl group. , n-heptyl, n-octyl, n-decyl, n-decyl, n-l-decyl, and n-d-decyl.

In the formula (11), R ¹³ is an alkylene group. With respect to R ¹³ , the number of carbon atoms of the alkyl group is preferably from 1 to 12, more preferably from 1 to 6, particularly preferably from 2 to 4. Preferred examples of R ¹³ include a vinyl group, a 1,2-vinyl group, a 1,1-vinyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, and a propane group. 1,1-diyl, propane-2,2-diyl, butane-1,4-diyl, butane-1,3-diyl, butane-1,2-diyl, butane-1 , 1-diyl, butane-2,2-diyl, butane-2,3-diyl, pentane-1,5-diyl, pentane-1,4-diyl, and hexane- 1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1,9-diyl, decane-1,10-diyl, undecane -1,11-diyl, and dodecane-1,12-diyl. Among these alkylene groups, preferred are 1,2-vinyl, propane-1,3-diyl, and butane-1,4-diyl.

Y is -NH-, -O, or -S-, preferably -NH-. Since the bond represented by -CO-NH- is less susceptible to hydrolysis than the bond represented by -CO-O- or -CO-S-, the Y-system is used in the photosensitive resin composition described later. The oxiran coupling agent which is -NH- is easy to form a pattern excellent in water resistance.

R ¹⁴ is a single bond or an alkylene group, preferably a single bond. A preferred example when R ¹⁴ is an alkylene group is the same as R ¹³ .

X is a nitrogen-containing heteroaryl group which may have a substituent and may be a single ring or a polycyclic ring, and the ring bonded to -YR ¹⁴ - in X is a nitrogen-containing 6-membered aromatic ring, -YR ¹⁴ - and A carbon atom in a 6-membered aromatic ring is bonded. Although the reason is not known, when a decane coupling agent having such X is used in the photosensitive resin composition described later, a pattern excellent in adhesion to a 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 monocyclic rings are condensed, or a group in which a plurality of monocyclic rings 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 from 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 contain a hetero atom or a hetero atom, and may be an aromatic ring or a non-aromatic ring.

Examples of the substituent which the nitrogen-containing heteroaryl group, that is, X, may have are an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkene having 2 to 6 carbon atoms. Base, alkoxy group having 2 to 6 carbon atoms, aliphatic fluorenyl group having 2 to 6 carbon atoms, benzamidine group, nitro group, nitroso group, amine group, hydroxyl group, mercapto group, cyano group, sulfonic acid group , a carboxyl group, a halogen atom, and the like. The number of substituents which X has is not particularly limited insofar as it does not impair the object of the present invention. The number of substituents which X has is preferably 5 or less, more preferably 3 or less. When X has a plurality of substituents, most of the substituents may be the same or different.

As a preferable example of X, the base of the following formula is mentioned.

Among the above groups, the group of the following formula is preferably X.

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

The content of the dispersing aid other than the above oxime ester compound is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 5% by mass, in the pigment dispersion liquid of the present invention.

[Preparation method of pigment dispersion]

The pigment dispersion liquid of the present invention can be mixed (dispersed and kneaded) with a pigment composed of a nitrogen-containing aromatic ring compound, a dispersant, the above-described oxime ester compound, and a solvent in a mixer such as a three-roll mill, a ball mill, or a sand mixer. It is prepared by filtering with a filter such as a 5 μm membrane filter as necessary. It is considered that in the preparation of the pigment dispersion liquid, the pigment composed of the nitrogen-containing aromatic ring compound and the above-mentioned oxime ester compound (as a dispersing aid) are first mixed (dispersed, kneaded) with a stirrer, and thus the nitrogen-containing aromatic ring is used. The π-π interaction between the pigment composed of the compound and the above oxime ester compound gives the effect of the present invention.

<Photosensitive resin composition>

The photosensitive resin composition of the present invention contains at least a base resin, a photopolymerization initiator, and a pigment dispersion of the present invention.

[Substrate Resin]

The base resin is not particularly limited, and examples thereof include known resins generally used in the photosensitive resin composition. The base resin can be used singly or in combination of two or more.

The base resin is, for example, a polymerizable resin containing a polymerizable base resin or the like. As such a polymerizable resin, among the alkali-soluble resins to be described later, those having an ethylenically unsaturated group are mentioned.

Further, examples of the base resin include an alkali-soluble resin. The alkali-soluble resin is a resin solution having a resin concentration of 20% by mass (solvent: Propylene glycol monomethyl ether acetate) was formed by forming a resin film having a thickness of 1 μm on a substrate and immersing it in a KOH aqueous solution having a concentration of 0.05% by mass for 1 minute, and having a thickness of 0.01 μm or more.

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

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

In the above formula (a-1), X ^a shows a group represented by the following formula (a-2).

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

Further, in the above 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 the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyl endomethylene tetrahydrophthalate. Anhydride, chloro-bromic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, and the like.

Further, in the above formula (a-1), Z ^a represents ^a residue from which two acid anhydride groups are removed from the tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and diphenyl ether tetracarboxylic dianhydride.

Further, in the above formula (a-1), m represents an integer of 0 to 20.

(A1) The mass average molecular weight of the resin having a fluorene structure, preferably from 1,000 to 40,000, more preferably from 2,000 to 30,000. By setting it in the said range, the favorable developability can be acquired, and sufficient heat resistance and film intensity are acquired.

Moreover, as another example of a suitable alkali-soluble resin, (A2) epoxy resin is mentioned. The (A2) epoxy resin is not particularly limited, and a known publicly known epoxy resin may be used, or an ethylenically unsaturated group may not be used, or an ethylenically unsaturated group may be used.

As the epoxy resin having no ethylenically unsaturated group, for example, at least an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound can be used for copolymerization. And the resin (A2-1).

Examples of the unsaturated carboxylic acid include monocarboxylic acids such as (meth)acrylic acid and crotonic acid; and dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and these dicarboxylic acids; Acid anhydride and the like. Among these, (meth)acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, ease of availability, and the like. These unsaturated carboxylic acids can be used individually or in combination of 2 or more types.

Further, in the present specification, "(meth)acrylic acid" means both acrylic acid and methacrylic acid.

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

The epoxy group-containing unsaturated compound may be one which does not have an alicyclic epoxy group, or which has an alicyclic epoxy group, but 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, and (meth)acrylic acid 3. (meth)acrylic acid epoxyalkyl group such as 4-epoxybutyl ester, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate Ester; α -glycidyl acrylate, glycidyl α -n-propyl acrylate, glycidyl α -n-butyl acrylate, α -ethyl acrylate 6,7-epoxyheptyl ester, etc. α - Alkyl acrylate alkyl acrylates; o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, glycidyl ethers such as p-vinylbenzyl glycidyl ether, and the like. Among these, from the viewpoints of copolymerization reactivity, strength of the resin after curing, and the like, glycidyl (meth)acrylate and 2-methylglycidyl (meth)acrylate are preferable. 6,7-epoxyheptyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.

The alicyclic group of the epoxy group-containing unsaturated compound having an alicyclic epoxy group may be a single ring or a polycyclic ring. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Further, examples of the polycyclic alicyclic group include a thiol group, an isoindole group, a tricyclic fluorenyl group, a tricyclic fluorenyl group, and a tetracyclic decyl 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, a compound represented by the following formula (a4-1) to (a4-6) is preferable, and the following formula (a4-1) is more preferable. ) a compound represented by ~(a4-4).

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, R ^a5 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10. As R ^a4 , a linear or branched alkyl group such as a vinyl group, a vinyl group, a propenyl group, a tetramethylalkenyl group, an ethylvinyl group, a pentenyl group or a hexamethylal group is preferable. R ^{a5 is} preferably, for example, a alkenyl group, a vinyl group, a propenyl group, a tetramethylalkenyl group, an ethylvinyl group, a pentenyl group, a hexamethyl group, a phenylene group, a cyclohexyl group, or a -CH ₂ -Ph group. -CH ₂ - (Ph represents a phenylene group).

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

The proportion of the constituent unit (constituting unit having an epoxy group) derived from the epoxy group-containing unsaturated compound in the resin (A2-1) is preferably 5 ~90 mass, more preferably 15~75 mass%. By being set in the above range, it becomes easy to form a color filter or the like having a good shape.

The resin (A2-1) is preferably a copolymerization of an alicyclic group-containing unsaturated compound.

The alicyclic group containing an alicyclic unsaturated compound may be a single ring or a polycyclic ring. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Further, examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isodecyl group, a tricyclodecyl group, a tricyclodecyl group, and a tetracyclododecyl group.

Specifically, examples of the alicyclic unsaturated group-containing 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, a compound represented by the following formula (a5-3) to (a5-8) is preferable, and the following formula (a5-3) is more preferable. ), a compound represented by (a5-4).

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 an alkyl group having 1 to 5 carbon atoms. R ^{a7 is} preferably a single bond, a linear or branched alkyl group such as a vinyl group, a vinyl group, a propenyl group, a tetramethyl group, an ethyl vinyl group, a pentenyl group, a hexamethylene group. base. As R ^a8 , for example, a methyl group or an ethyl group is preferable.

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

Further, the resin (A2-1) may be further copolymerized with other compounds than the above. As such other compounds, mention may be made (Meth) acrylates, (meth) acrylamides, allylic compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds can be used singly or in combination of two or more.

Examples of the (meth) acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, and (meth)acrylic acid. Linear or branched alkyl (meth)acrylate such as octyl ester; chloroethyl (meth)acrylate, 2,2-dimethylhydroxypropyl (meth)acrylate, (methyl) 2-hydroxyethyl acrylate, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate, decyl (meth)acrylate, and the like.

Examples of the (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, and N, N-di. Alkyl (meth) acrylamide, N,N-aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N- Base (meth) acrylamide and the like.

Examples of the allyl compound include allyl acetate, allyl hexanoate, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, and B. Allyl acetate such as allyl acetate and allyl lactate; allyloxyethanol and the like.

Examples of the vinyl ethers include hexyl vinyl ether, octyl vinyl ether, mercapto vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, and ethoxyethyl vinyl ether. , chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether , dimethylamine ethyl vinyl ether, diethylamine An alkyl vinyl ether such as ethyl vinyl ether, butylamine ethyl vinyl ether, benzyl vinyl ether or tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chloride A vinyl aryl ether such as phenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether or vinyl decyl ether.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, and Vinyl chloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenyl acetate, vinyl acetate, vinyl lactate, vinyl β -phenylbutyrate, vinyl benzoate, vinyl urate Ester, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

Examples of the styrene include styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, and butyl styrene; Alkenyl styrene, cyclohexyl styrene, mercapto styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, ethoxymethyl methyl styrene Styrene; alkoxystyrene such as methoxystyrene, 4-methoxy-3-ethylstyrene, dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, Tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3 - Halogen styrene such as trifluoromethyl styrene.

The mass average molecular weight of the resin (A2-1) is preferably from 2,000 to 50,000, more preferably from 5,000 to 30,000. In the above range, it is easy to obtain a film forming ability and a balance of developability of the photosensitive resin composition. to.

On the other hand, as the 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-containing unsaturated group can be used. a resin (A2-2) obtained by reacting an epoxy group of a compound, or an epoxy group of a resin obtained by polymerizing at least an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound, and an unsaturated carboxylic acid The resin obtained by the reaction of the carboxyl group (A2-3).

The unsaturated carboxylic acid or the epoxy group-containing unsaturated compound may, for example, be a compound exemplified as the above resin (A2-1). 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 ratio of the constituent unit (having a constituent unit having a carboxyl group) derived from the unsaturated carboxylic acid in the resins (A2-2) and (A2-3) is preferably 5 to 60% by mass, more preferably 10 to 40% by mass. . By setting it in the said range, the developability of the photosensitive resin composition can be suitably.

In addition, the ratio of the constituent unit (the constituent unit having an epoxy group) derived from the epoxy group-containing unsaturated compound in the resin (A2-2) or (A2-3) is preferably 5 to 90% by mass, more preferably Good is 15~75% by mass. By being set in the above range, it becomes easy to form a color filter or the like having a good shape.

The mass average molecular weight of the resins (A2-2) and (A2-3) is preferably from 2,000 to 50,000, more preferably from 5,000 to 30,000. By setting it in the said range, it is easy to acquire the film formation ability of the photosensitive resin composition, and the balance of developability.

In addition to the above, as (A2) epoxy resin, it is also possible to use double Phenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol type or cresol novolac type epoxy resin, resol type epoxy resin, triphenylmethane type An epoxy group of an epoxy resin, a polycarboxylic acid polyglycidyl ester, a polyhydric alcohol polyglycidyl ester, an amine epoxy resin, or a dihydroxybenzene type epoxy resin, and reacted with (meth)acrylic acid An epoxy group (meth)acrylic resin or the like.

The content of the base resin is preferably from 40 to 85% by mass, more preferably from 45 to 75% by mass, based on the solid content of the photosensitive resin composition. By setting it in the said range, it is easy to acquire the balance of developability.

[Photopolymerization initiator]

The photopolymerization initiator is not particularly limited, and a conventionally known photopolymerization initiator can be used. The photopolymerization initiator can be used singly or in combination of two or more.

Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-[4-(2-hydroxyl). Ethoxy)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)one, 2,4,6-trimethylbenzene Methyl phenyl diphenyl phosphine oxide, 4-benzylidene-4'-methyl dimethyl sulfide, 4-dimethylamine benzoic acid, methyl 4-dimethylamine benzoate, 4-di Ethyl methylamine benzoate, butyl 4-dimethylaminebenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isopentylbenzoic acid , benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) fluorene, o-benzidine Methyl benzoate, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone , thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylhydrazine, octadecyl Base, 1,2-benzopyrene, 2,3-diphenylanthracene, azobisisobutyronitrile, benzammonium peroxide, cumene peroxide, 2-mercaptobenzene Imidazole, 2-mercaptobenzophenone Azole, 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 (i.e., mireconone), 4,4'-bisdiethylaminobenzophenone (i.e., ethyl mizirone), 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-pair Methylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyl acetophenone, p-dimethylaminoacetophenone, p-tertiary butyl trichloroacetophenone, three-stage Butyl dichloroacetophenone, α ,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone , 2-isopropylthioxanthone, dibenzosuberone, amyl 4-dimethylaminobenzoate, 9-phenyl acridine, 1,7-bis-(9-acridinyl) Heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-para (three Chloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl -4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three Oxazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3 ,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis (three Chloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxybenzene -4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-three Pyrazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3- Bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo 4-methoxy)styrylphenyl-s-triazine, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl ]-, 1-(O-acetamidine), 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylidenehydrazine), 2-benzyl Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one, 2 -Methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one, "NCI-831" (trade name: manufactured by ADEKA CORPORATION). Further, the oxime ester compound used in the present invention, that is, an oxime ester compound bonded to an aromatic hydrocarbon ring or an aromatic heterocyclic ring via a carbon atom containing an aromatic ring and a carbonyl group, is contained in a carbon atom contained in the fluorenyl group. It can also be used as a photopolymerization initiator. In other words, in the photosensitive resin composition of the present invention, the oxime ester compound is contained not only as a dispersing aid but also as a dispersing aid in the pigment dispersion liquid, and also as a photopolymerization. It is included as a starter. At this time, the oxime ester compound as a photopolymerization initiator is considered to have no π-π interaction with the pigment composed of the nitrogen-containing aromatic ring compound. The oxime ester compound as a photopolymerization initiator is preferably a compound represented by the above formula (1) as described above.

The content of the photopolymerization initiator is preferably from 0.5 to 20% by mass based on the solid content of the photosensitive resin composition. By setting it in the said range, it can obtain sufficient heat resistance and chemical-resistance, and can improve a coating film formation ability, and can suppress a hardening defect.

In addition, when the photosensitive resin composition contains the oxime ester compound as a photopolymerization initiator, the ratio of the oxime ester compound is preferably from 1 to 100% by mass, more preferably from 1 to 100% by mass based on the total amount of the photopolymerization initiator. 20 to 100% by mass, and more preferably 50 to 100% by mass, particularly preferably 80 to 100% by mass. Since it is set in the above range, the sensitivity or fine line adhesion of the photosensitive resin composition can be improved.

[Pigment dispersion]

The content of the pigment dispersion liquid of the present invention is appropriately determined depending on the use of the photosensitive resin composition. As an example, the content of the pigment in the photosensitive resin composition is preferably based on the solid content of the photosensitive resin composition. The amount is 5 to 70% by mass, more preferably 25 to 60% by mass.

In the case of using the photopolymerizable monomer described later, the content of the pigment dispersion liquid in the photosensitive resin composition of the present invention is 100% of the total amount of the base resin and the photopolymerizable monomer. The mass portion is preferably an amount of from 0.01 to 2.5 parts by mass, more preferably from 0.01 to 0.5 parts by mass. By adjusting the content of the pigment dispersion liquid of the present invention in order to bring the content of the above-mentioned oxime ester compound into the relevant range in the photosensitive resin composition, it is easy to form a fine pattern excellent in adhesion to the substrate.

[Photopolymerizable monomer]

The photosensitive resin composition of the present invention may further contain a photopolymerizable monomer. The photopolymerizable monomer is not particularly limited, and a conventionally known monofunctional monomer or polyfunctional monomer can be used. The photopolymerizable monomer can be used singly or in combination of two or more.

Examples of the monofunctional monomer include (meth)acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, and ethoxymethyl (methyl). Acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyl Base (meth) acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-propene oxime Amine-2-methylpropanesulfonic acid, tertiary butyl propylene sulfonamide, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate 2 -ethylhexyl ester, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (A) 2-phenoxy-2-hydroxypropyl acrylate, 2-(methyl)propenyloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, (methyl) Tetrahydrofurfuryl acrylate, dimethylamine (meth)acrylate, glycidyl (meth)acrylate, (A) ) 2,2,2-trifluoroethyl acrylate, ethyl (meth) acrylate, 2,2,3,3-tetrafluoro-propyl, semi-phthalic acid derivative of (meth) acrylate. These monofunctional monomers can be used singly or in combination of two or more.

On the other hand, as a polyfunctional monomer, ethylene glycol di(A) Acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, dibutyl Alcohol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, two (meth)acrylic acid glyceride, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol IV (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis(4-(methyl) propylene decyloxy diethoxy phenyl) Propane, 2,2-bis(4-(methyl)propenyloxypolyethoxyphenyl)propane, 2-hydroxy-3-(methyl)propenyloxypropyl (meth) acrylate, Ethylene glycol diglycidyl ether di(meth) acrylate, diethylene glycol diglycidyl ether di(meth) acrylate, phthalic acid diglycidyl Di(meth)acrylate, glyceryl triacrylate, glycerol polyglycidyl ether poly(meth) acrylate, urethane (meth) acrylate (ie, phenylphenyl diisocyanate), Reaction of trimethylhexamethylene diisocyanate with hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate, methylene bis(meth) acrylamide, (meth) acrylamide a polyfunctional monomer such as a condensate of methylene ether, a polyhydric alcohol and N-methylol (meth) acrylamide, or 1,3,5-tripropenyl hexahydro-1,3,5-tri Triacrylformal and the like. These polyfunctional monomers can be used singly or in combination of two or more.

The content of the photopolymerizable monomer is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass, based on the solid content of the photosensitive resin composition. By In the above range, it tends to be easy to obtain the balance of sensitivity, developability, and resolution.

[Other ingredients]

The photosensitive resin composition may contain various additives as necessary. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, a deagglomerating agent, a thermal polymerization inhibitor, an antifoaming agent, and a surfactant.

<Method for Producing Photosensitive Resin Composition>

The method for producing a photosensitive resin composition of the present invention comprises at least a step of mixing a base resin, a photopolymerization initiator, and the pigment dispersion of the present invention. In this step, a photopolymerizable monomer and/or other components may be mixed in addition to the above components. These components can be mixed by a mixer such as a three-roll mill, a ball mill, or a sand mixer. Further, in order to make the produced photosensitive resin composition uniform, it is also possible to filter using a filter such as a 5 μm membrane filter.

In the method for producing a photosensitive resin composition of the present invention, a pigment dispersion liquid composed of a nitrogen-containing aromatic ring compound, a dispersant, the above-described oxime ester compound, and a solvent are prepared in advance to prepare a pigment dispersion liquid, and the pigment dispersion liquid and the base resin are prepared. Mix other ingredients. By such a procedure, a photosensitive resin composition capable of forming a fine pattern having high adhesion even at a low exposure amount can be obtained.

[Examples]

Hereinafter, the invention will be more specifically described by way of examples, but the scope of the invention is not limited to the examples.

In the following examples and comparative examples, the following compound 1 and comparative compounds 1 to 4 were used as the oxime ester compound.

<Synthesis of oxime ester compounds>

Hereinafter, the synthesis of the compound 1 will be described by Synthesis Example 1.

[Synthesis Example 1]

2-(2-methylphenyl)-1-[4-(phenylhydrazino)phenyl]ethane-1,2- 7.68 g (23.13 mmol) of diketone, 2.93 g (42.16 mmol) of hydroxylamine hydrochloride, and 4.15 g (41.01 mmol) of triethylamine were mixed in 64.00 g of ethanol, and reacted at 75 ° C to 80 ° C for 3 hours. The reaction solution was evaporated, ethyl acetate was added, washed with brine, and dried over anhydrous magnesium sulfate and evaporated to give 2-(2-methylphenyl)2-(N-hydroxyimino)-1- 4-(phenylhydrazino)phenyl]ethane-1-one 8.03 g. 8.03 g of 2-(2-methylphenyl)-2-(N-hydroxyimino)-1-[4-(phenylhydrazino)phenyl]ethane-1-one obtained in acetic acid 13.33 g (130.57 mmol) of acetic anhydride was acetonitrile, and 6.25 g of the 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, the dispersing agent, and the hydrazine compound shown in Table 1 were mixed and dissolved in the solvent shown in Table 1, to prepare a pigment dispersion liquid having a solid concentration of 17 to 23% by mass. In addition, the amount of each component used is as shown in Table 1. Further, the details of the pigment, the dispersant, and the solvent are as follows. The mixture 1 of Example 10 is a mixture (mass ratio of 1:1) of the above-mentioned synthesized compound 1 (an oxime ester compound) and a decane coupling agent having a nitrogen-containing aromatic ring represented by the following formula.

‧pigment

R254 (C.I. Pigment Red 254, diketoppyrrolopyrrole pigment represented by the leftmost formula below)

B15:6 (C.I. Pigment Blue 15:6, which is represented by the following central formula)

G58 (C.I. Pigment Green 58, 酞Cyanine pigment expressed by the following rightmost formula)

Perylene (3,4,9,10-decanetetracarboxylic acid diimine: in the above formula (e-3), R ^e7 and R ^e8 are hydrogen atoms)

‧Dispersant

Acrylic resin-based polymer dispersant (trade name: DisperBYK2001, manufactured by BYK)

‧Solvent

Mixed solvent of 3-methoxybutyl acetate / propylene glycol monomethyl ether acetate = 60 / 40 (mass ratio)

[Evaluation of viscosity]

Using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) to measure immediately after preparation The viscosity of the pigment dispersion. Further, the pigment dispersion liquid was filled in a light-shielding glass container, and after standing at 40 ° C for 7 days in a sealed state, the viscosity of the pigment dispersion liquid 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 was 0.3 mPa ‧ s or less, it was judged that the dispersion stability of the pigment dispersion liquid was good (○), and the difference was more than 0.3 mPa ‧ s At the time, it was judged that the dispersion stability of the pigment dispersion liquid was poor (x). The results are shown in Table 1.

As shown in Table 1, in Examples 1, 2, and 4 to 10, since the addition of the compound 1, even if the content of the dispersant was reduced, the dispersion stability of the pigment was good. it is good. On the other hand, in Comparative Examples 1 to 10 in which Compound 1 was not used, when a large amount of dispersant was used in Examples 1, 2, and 4 to 10, the dispersion stability of the pigment was good, or even if it was used, it was implemented. In the examples 1, 2, and 4 to 10, a large amount of dispersant has poor dispersion stability of the pigment. From the above, it is understood that the pigment dispersion liquid of the present invention has good dispersion stability of the pigment even if 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 the resin A (solid content: 55 mass%, solvent: 3-methoxybutyl acetate), and 30 parts by mass of dipentaerythritol hexaacrylate, And the pigment dispersion liquid of Table 2 (solid content concentration of each pigment dispersion liquid is 17-23 mass %, pigment content is 15 mass %.) 100 mass parts, and 3-methoxy butyl acetate. (60% by mass) was mixed with a mixed solvent of propylene glycol monomethyl ether acetate (40% by mass), and then filtered through a membrane filter having a pore size of 5 μm to prepare a photosensitive resin composition. Further, the amount of the mixed solvent was adjusted, and the solid content concentration in the photosensitive resin composition was adjusted to 15% by mass.

Further, among the photopolymerization initiators shown in Table 2, the details of "OXE01" and "Compound 1 + OXE01" are as follows.

OXE01: Photopolymerization initiator manufactured by BASF Co., Ltd. (trade name: IRGACURE OXE 01: 1.2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylidene)) )

Compound 1 + OXE01: a mixture of Compound 1 and OXE01 (mass Than 1:1)

Moreover, the resin A used for preparation of the photosensitive resin composition was synthesized based on the following points.

First, 235 g of a bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, and 100 mg of 2,6-di-tert-butyl-4-methylphenol were placed in a 500 ml four-necked flask. And 72.0 g of acrylic acid, which was blown at a rate of 25 ml/min while being dissolved by heating at 90 to 100 °C. Next, the solution was slowly warmed up in a white turbid state, and heated to 120 ° C to be completely dissolved. At this point, although the solution gradually became transparent and viscous, it continued to stir as it was. During this period, the acid value was measured, and heating and stirring were continued until it was less than 1.0 mgKOH/g. It takes 12 hours for the acid price to reach the target value. Then, it was cooled to room temperature to obtain a bisphenolphthalein type epoxy acrylate represented by the following structural formula (a-4) as a colorless transparent and solid.

Next, after dissolving 600 g of 3-methoxybutyl acetate in 307.0 g of the above-mentioned bisphenolphthalein type epoxy acrylate thus obtained, 80.5 g of benzophenone tetracarboxylic dianhydride and bromine were mixed. 1 g of tetraethylammonium was slowly reacted 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 the reaction was carried out at 90 ° C for 6 hours to obtain a resin A. The disappearance of the acid anhydride group was confirmed by infrared spectroscopy. This resin A corresponds to the compound represented by the above formula (a-1).

The photosensitive resin composition of each of Examples 11 to 24 and Comparative Examples 11 to 21 was evaluated for coloring by post-baking and evaluation of fine line adhesion by the following method. The results are shown in Table 2.

[coloring evaluation]

The photosensitive resin compositions of the respective Examples 11 to 24 and Comparative Examples 11 to 21 were subjected to coloring evaluation according to the following procedure.

First, a 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 coating film of 1.0 μm on the surface of the glass substrate. Thereafter, using a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Corporation), the exposure amount was set to 20, 50, 100, or 200 mJ/cm ² , and the exposure gap was set. The coating film was exposed at 200 μm. 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. For the coating film before and after the post-baking, an instantaneous multi-photometric system (MCPD-3000: manufactured by Otsuka Electronics Co., Ltd.) was used, and the difference between the transmittances in the wavelength range of 380 nm to 780 nm was measured as ΔY. The value of ΔY is shown in Table 2. The smaller the absolute value of ΔY, the more it means that it is not colored.

[Evaluation of fine line adhesion]

The photosensitive resin compositions of Examples 11 to 24 and Comparative Examples 11 to 21 were applied onto a glass substrate (100 mm × 100 mm) using a spin coater, and prebaked at 90 ° C for 120 seconds to form a film thickness of 1.0 μm. Coating film. Next, using a mirror projection alignment exposer (product name: TME-150RTO, manufactured by Topcon Corporation), the exposure gap was set to 50 μm, and the coating film was irradiated with ultraviolet rays through a negative image mask which forms a line pattern of 5 μm. The exposure amount was set to four stages of 20, 50, 100, and 200 mJ/cm ² . After the exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26 ° C for 40 seconds, it was post-baked at 230 ° C for 30 minutes to form a line pattern.

The line pattern formed by observing the line pattern by an optical microscope was evaluated. The fine line adhesion was evaluated as "good" when the line pattern was not peeled off from the substrate, and it was evaluated as "poor" when the substrate was not peeled off and the line pattern was not formed. 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 was suppressed, and a line pattern of 5 μm was adhered to the substrate at an exposure amount of 50 mJ/cm ² . In particular, in Examples 12 to 15, and 17 to 24, the line pattern of 5 μm was 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, the coloring by heating during post-baking can be suppressed, but the line pattern of 5 μm is not adhered to the substrate at an exposure amount of 50 mJ/cm ² . In the comparison of Examples 11 to 24, the fine line adhesion was poor.

Further, in Comparative Examples 12, 13, 20, and 21, a line pattern of 5 μm was adhered to the substrate at an exposure amount of 50 mJ/cm ² , particularly in Comparative Examples 12, 20, and 21, even at 20 mJ/cm. ² such a low exposure amount, the line pattern of 5 μm is still in close contact with the substrate. However, in Comparative Examples 12, 13, 20, and 21, the coloring caused by the heating at the time of post-baking could not be suppressed. The photosensitive resin composition of Comparative Example 12 or 13 contains Compound 1 as a photopolymerization initiator, but since it cannot suppress coloring, it is considered that between Compound 1 and a pigment composed of a nitrogen-containing aromatic ring compound, No π-π interaction is produced.

Further, in Comparative Examples 16, 18, and 19, coloring due to heating during post-baking could not be suppressed, and a line pattern of 5 μm was not adhered to the substrate at an exposure amount of 50 mJ/cm ² , and Examples 11 to 24 In comparison, fine lines are less adherent.

Claims (6)

A pigment dispersion liquid comprising a pigment, a dispersant, an oxime ester compound and a solvent composed of a nitrogen-containing aromatic ring compound, wherein the oxime ester compound is a carbon atom contained on a sulfhydryl group, via an organic group containing an aromatic ring And a carbonyl group, which is bonded to an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The pigment dispersion liquid according to claim 1, wherein the oxime ester compound is an oxime ester compound represented by the following formula (1): (wherein R ¹ represents an aryl group which may have a substituent, 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 a carbon number of 1 to 6 Alkyl). The pigment dispersion liquid according to claim 2, wherein the R ² is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent. A photosensitive resin composition containing a base resin, a photopolymerization initiator, and a pigment dispersion liquid according to claim 1. a dispersing aid consisting of an oxime ester compound, the aforementioned oxime ester compound The carbon atom contained in the fluorenyl group is bonded to an aromatic hydrocarbon ring or an aromatic heterocyclic ring via an organic group and a carbonyl group containing an aromatic ring. The dispersing aid according to claim 5, wherein the oxime ester compound is an oxime ester compound represented by the following formula (1): (wherein R ¹ represents an aryl group which may have a substituent, 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 a carbon number of 1 to 6 Alkyl).