KR20150016898A - Pigment dispersion, photosensitive resin composition therewith, and dispersion aids - Google Patents

Abstract

Provided is a pigment dispersed liquid, a photosensitive resin composition including the same, and a dispersion aid. The pigment dispersed liquid can impart a photosensitive resin having good pigment dispersion stability even when the content of a dispersing agent is reduced, and high adhesion fine patterns can be produced even with a low amount of exposure. The pigment dispersed liquid of the present invention contains a pigment consisting of a nitrogen-containing aromatic ring compound, a dispersing agent, an oxime ester compound, and a solvent. The oxime ester compound is coupled with an organic group including an aromatic ring in a carbon atom included in an oxime group and with an aromatic hydrocarbon ring or an aromatic heterocyclic ring through a carbonyl group. The photosensitive resin composition of the present invention includes a base material resin, a photopolymerization initiator, and the aromatic heterocyclic ring. The dispersion aid of the present invention consists of the oxime ester compound.

Description

PIGMENT DISPERSION, PHOTOSENSITIVE RESIN COMPOSITION THEREWITH, AND DISPERSION AIDS [0002]

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

The liquid crystal panel is provided with a black matrix for emphasizing the contrast of an image or a color filter in which R, G, and B colored layers of red (R), green (G) and blue (B) are formed. These black matrixes and color filters are formed by applying and drying a photosensitive resin composition in which black or pigments of respective colors are dispersed on a substrate, and then exposing and developing the resulting coating film to form a desired pattern. In order to produce such a photosensitive resin composition, a pigment dispersion in which a pigment is dispersed is used. For example, Patent Document 1 discloses a pigment dispersion containing a pigment, a solvent, a dispersant, and a specific additive having an azo group, an amide group and a carbonyl group.

Japanese Patent Laid-Open Publication No. 2012-087233

In recent years, technical innovations have been made in increasing the resolution of a liquid crystal panel, and it is required to improve the coloring property of the RGB coloring layer. In the photosensitive resin composition for imparting the RGB coloring layer, the coloring property can be improved by increasing the concentration of the pigment. However, since the high concentration of the pigment causes a decrease in the sensitivity of the photosensitive resin composition to light, it becomes difficult to form a pattern having a good shape at a low exposure amount, for example, and productivity in the exposure step tends to be lowered.

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

Disclosure of the Invention The present invention has been made in view of such conventional circumstances, and it is an object of the present invention to provide a pigment dispersion which can impart a photosensitive resin composition capable of forming a fine pattern with high adhesion even at a low exposure dose, And to provide a photosensitive resin composition and a dispersion aid containing the same.

The present inventors have intensively studied and found that the above problems can be solved by adding a specific oxime ester compound to a pigment dispersion containing a pigment comprising a nitrogen-containing cyclic compound, and have completed the present invention. Specifically, the present invention provides the following.

A first aspect of the present invention is a color photographic light-sensitive material comprising a pigment comprising a nitrogen-containing aromatic ring compound, a dispersing agent, an oxime ester compound and a solvent, wherein the oxime ester compound has an organic group containing an aromatic ring at a carbon atom contained in the oxime group, An aromatic hydrocarbon ring or an aromatic heterocyclic ring is bonded through a carbonyl group.

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

The third aspect of the present invention is a dispersion auxiliary comprising an oxime ester compound wherein the oxime ester group is an aromatic hydrocarbon ring or an aromatic heterocyclic ring bonded through an organic group having an aromatic ring and a carbonyl group to a carbon atom contained in the oxime group .

According to the present invention, there can be provided a pigment dispersion capable of imparting a photosensitive resin composition capable of forming a fine pattern of high adhesion even at a low exposure dose with good dispersion stability of the pigment even if the content of the dispersant is reduced, a photosensitive resin composition containing the same, Can be provided.

<Pigment dispersion>

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

[Pigment made of nitrogen-containing ring compound]

The pigment dispersion according to the present invention contains a pigment comprising a nitrogen-containing aromatic ring compound. The pigment dispersion according to the present invention is preferably used for the formation of color filters, paints, solder resistors, ink jet inks and the like of liquid crystal display displays, for example, by containing such pigments. These pigments may be used alone or in combination of two or more.

Examples of pigments made of nitrogen-containing aromatic ring compounds include, but are not limited to, diketopyrrolopyrrole pigments, phthalocyanine pigments, perylene pigments, azo pigments, quinacridone pigments, benzimidazolone pigments, Isoindolinone pigments, dioxazine pigments, indanthrene pigments and the like, and it is preferable to use diketopyrrolopyrrole pigments, phthalocyanine pigments and / or perylene pigments.

The diketopyrrolopyrrole pigment is not particularly limited and includes, for example, a compound represented by the following formula (b-1).

In formula (b-1), A ³ and A ⁴ each independently represent a halogen atom, a methyl group, an ethyl group, a tert-butyl group, a phenyl group, an N, N-dimethylamino group, a trifluoromethyl group or a cyano group, k 'each independently represent an integer of 0 to 5, and when k and k' are each an integer of 2 or more, a plurality of A ³ and A ⁴ 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, it is preferable that k and k 'are each independently an integer of 0 to 3 in order to attain high contrast and easily adjust a red color suitable for a color filter, and k and k' are each independently 0 or 1 Is more preferable.

As the diketopyrrolopyrrole-based pigment, a color filter having a high luminance and a high contrast can be formed. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I. Pigment Red 270, C.I. Pigment Red 272, C.I. Pigment Orange 71, C.I. Pigment Orange 73 is preferable, and C.I. Pigment Red 254, C.I. Pigment Red 255 is more preferable. The diketopyrrolopyrrole pigments may be used singly 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. In order to improve the contrast, the thickness is preferably within a range of 10 to 50 nm, and more preferably within a range of 10 to 30 nm. Since the average primary particle size of the pigment is in the above-mentioned range, for example, the color filter can be made to have high consistency and high quality. In addition, the average particle diameter of the pigment can be obtained by a method of directly measuring the size of primary particles from an electron microscope photograph. More specifically, the short axis diameter and the major axis diameter of each primary particle are measured and the average thereof is defined as the particle diameter of the particle. Subsequently, the particle volume (weight) of each of the 100 or more particles is determined approximately in parallel with the obtained rectangular parallelepiped, and the volume average particle diameter is obtained, and the average particle diameter is obtained. In addition, the same result can be obtained by using either a transmission type (TEM) or a scanning type (SEM) as an electron microscope.

The diketopyrrolopyrrole pigment used in the present invention can be produced by a known method such as recrystallization, solvent salt milling and the like. A commercially available diketopyrrolopyrrole pigment may also be used.

The phthalocyanine-based pigment is not particularly limited and includes, for example, a compound represented by the following formula (b-2).

X _{1 to} X ₄ each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, 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 an arylthio group which may have a substituent. Y _{1 to} Y ₄ each independently represent a halogen atom, a nitro group, a phthalimidemethyl group which may have a substituent or a sulfamoyl 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 + , They may be the same or 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, a cycloalkyl group which may have a substituent, , An alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, and an arylthio group which may have a substituent. In the case where X _{1 to} X ₄ have a substituent, the substituents may be the same or different. Specific examples thereof include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a characteristic group such as an amino group, a hydroxyl group and a nitro group, An alkyl group, an aryl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, an alkylthio group, and an arylthio group. These substituents may be plural.

The "alkyl group" of the alkyl group which may have a substituent includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, Ethylhexyl group and the like, and examples of the "alkyl group having a substituent" include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-di 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butyl Benzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and the like.

Examples of the "aryl group" of the aryl group which may have a substituent include a phenyl group, a naphthyl group and an anthryl group, and examples of the "aryl group having a substituent" include p-methylphenyl group, p- naphthyl group, a 4-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxyphenylphenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, 2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group, and the like.

Examples of the "cycloalkyl group" of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group and an adamantyl group. Examples of the "cycloalkyl group having a substituent" include 2,5-dimethylcyclopentyl group, 4-tert -Butylcyclohexyl group and the like.

The "heterocyclic group" of the heterocyclic group which may have a substituent includes a pyridyl group, a pyradyl group, a piperidino group, a pyranyl group, a morpholino group and an acridinyl group, and the "heterocyclic group having a substituent" 3-methylpyridyl group, N-methylpiperidyl group, N-methylpyrrolyl group and the like.

Examples of the "alkoxyl group" of the alkoxyl group which may have a substituent include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, A straight chain or branched alkoxyl group such as dimethyl-3-pentyloxy, n-hexyloxy group, n-octyloxy group, stearyloxy group and 2-ethylhexyloxy group, Include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditrifluoromethyl group A 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, and a benzyloxy group.

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

Examples of the "alkylthio group" of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, , And octadecylthio group. Examples of the "alkylthio group having a substituent" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethyl group And so on.

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

Next, Y ₁ ~Y Specific examples of the _four cases is the phthalimide which may have a halogen atom, a nitro group, an optionally substituted imide group _{(C 6 H 4 (CO)} 2 N-CH 2 -), sulfonic peomo group (H ₂ NSO ₂ -). Also, a phthalimido methyl group having a substituent represents a structure in which a hydrogen atom in a phthalimide methyl group is substituted by a substituent, and a sulfamoyl group having a substituent means a structure in which a hydrogen atom in a sulfonyl group is substituted by a substituent. Preferred Y _{1 to} Y ₄ are a halogen atom and a sulfamoyl group. The phthalocyanine compound m1~m4 (without i.e., Y ₁ ~Y ₄₎ 0 which may be preferably used. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The "substituent" of the phthalimido methyl group which may have a substituent and the sulfamoyl group which may have a substituent is the same as the substituent of X _{1 to} X ₄ .

The phthalocyanine pigments include C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Pigment Green 58, C.I. Pigment Blue 16, C.I. Pigment Blue 75 and C.I. Pigment Blue 15 (including 15: 1 to 15: 6 and the like), and the like, and C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Blue 15: 1 to 15: 6 is more preferable. The phthalocyanine pigments may be used singly or in combination of two or more kinds.

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

Examples of the perylene pigments include perylene pigments represented by the following formula (e-1), perylene pigments represented by the following formula (e-2) and perylene pigments represented by the following formula (e-3) . As commercial products, the products K0084 and K0086 manufactured by BASF, or Pigment Black 21, 30, 31, 32, 33 and 34 may be suitably used as a perylene 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 acetyl 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 are each independently 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 alkyl groups, the alkyl groups may be linear or branched.

Examples of the compound represented by the formula (e-1), the compound represented by the formula (e-2) and the compound represented by the formula (e-3) -26784 publication or the like. That is, a heating reaction is conducted in water or an organic solvent using perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines as raw materials. The target product can be obtained by reprecipitation of the obtained preparation in sulfuric acid or recrystallization in water, an organic solvent or a mixed solvent thereof.

In order to disperse the perylene-based pigment well, the average particle diameter of the perylene-based pigment is preferably 10 to 1000 nm.

In the pigment dispersion according to the present invention, a pigment made of a nitrogen-containing aromatic ring compound having a color tone 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, , Violet pigments such as 31, 32, 36, 37, 38, 39, 42, 44, 47, 49, 50, Solvent Violet 13,

C.I. Pigment Orange 1, 2, 5, 13, 14, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 40, 43, 46, 48, 49, 51, 61 , Orange pigments such as 62, 63, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77,

C.I. Brown pigments such as Pigment Brown 23 and 25,

C.I. Yellow pigments such as Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 and 185 can be mentioned.

The content of the pigment comprising the nitrogen-containing cyclic compound is preferably 5 to 95% by weight, more preferably 25 to 90% by weight based on the solid content of the pigment dispersion according to the present invention.

[Dispersant]

The pigment dispersion according to the present invention contains a dispersant. When the pigment dispersion contains a dispersant, the pigment is easily dispersed uniformly in the pigment dispersion. The dispersant may be used alone or in combination of two or more.

As the dispersion agent, known ones may be used, and it is preferable to use a polyethyleneimine-based polymer dispersant, a urethane resin-based polymeric dispersant, and an acrylic resin-based polymeric dispersant.

In the pigment dispersion according to the present invention, the content of the dispersant is preferably 1 to 50 parts by weight, more preferably 1 to 20 parts by weight, and further preferably 1 to 15 parts by weight based on 100 parts by weight of the pigment. If the content of the dispersant is within the above range, the pigment can be uniformly dispersed in the pigment dispersion according to the present invention more easily. In addition, the smaller the upper limit, the more easily the balance of the respective components in the photosensitive resin composition described later is improved, so that the blending amount of the other components in the photosensitive resin composition can be relatively increased, do. The effect of using a blue pigment which absorbs the light of a particular wavelength is improved with respect to the sensitivity characteristic.

[Oxime ester compound]

The pigment dispersion according to the present invention contains an oxime ester compound in which an aromatic hydrocarbon ring or aromatic heterocyclic ring is bonded to an organic group containing an aromatic ring and a carbonyl group at a carbon atom contained in the oxime group. This oxime ester compound has a function as a photopolymerization initiator and a function as a dispersing aid. Therefore, when the pigment dispersion containing the pigments of the nitrogen-containing ring compound is contained in the oxime ester compound, the dispersion stability of the pigment tends to be good even if the content of the dispersant is reduced. That is, by using the oxime ester compound, it becomes easy to reduce the content of the dispersant in the pigment dispersion without impairing the dispersion stability of the pigment. As a result, a part of the dispersing agent is substituted with the oxime ester compound. Since the oxime ester compound also functions as a photopolymerization initiator, the above substitution is equivalent to reducing the content of the dispersant and increasing the content of the photopolymerization initiator. Therefore, in the photosensitive resin composition obtained from the pigment dispersion containing the oxime ester compound, the content of the photopolymerization initiator can be increased, and it becomes easy to form a high-adhesion small pattern at a low exposure amount from the photosensitive resin composition. These oxime ester compounds may be used alone or in combination of two or more.

In a pigment made of a nitrogen-containing cyclic compound, the? -Electro-system is in an unstable state as compared with the case where a nitrogen atom is not contained due to the influence of nitrogen atoms contained in the molecule. As a result, the pigments made of the nitrogen-containing cyclic compound are less likely to have good dispersion stability. The oxime ester compound used in the pigment dispersion according to the present invention contains an oxime group and a carbonyl group, and since a ring is bonded to these groups, a stable pi electron system is formed. It is presumed that the π-π interaction occurs between the oxime ester compound and the pigments comprising the nitrogen-containing cyclic compound and the molecules of each other are stacked to stabilize the π electromagnetic field of the pigment. As a result, it is considered that the oxime ester compound can improve the dispersion stability of a pigment comprising a nitrogen-containing aromatic ring compound.

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

In the oxime ester compound, the organic group including an aromatic ring is not particularly limited, and examples thereof include an aryl group which may have a substituent. In the following the aryl group which may have a substituent may include groups exemplified with respect to R ¹ in the formula (1).

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

Examples of the oxime ester compound include oxime ester compounds represented by the following formula (1).

(Wherein, R ¹ represents an aryl group which may have a substituent, R ² represents a heteroaryl group which may have a substituent or an aryl group which may have a substituent, R ³ is a hydrogen atom or an alkyl group of carbon number 1 to 6 Lt; / RTI &gt;

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

In R ¹ , the substituent that the aryl group or the phenyl group may have is not particularly limited within the scope of not impairing the object of the present invention. Examples of preferable substituents which the phenyl group may have include an alkyl group, an alkoxyl group, a cycloalkyl group, a cycloalkoxyl group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, a phenyl group which may have a substituent, , A phenylthio group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, A naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, A heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, one or two amino groups There may be mentioned an amino group, a morpholin-1-yl group, piperazin-1-yl group, a halogen atom, a nitro group and a cyano group substituted with an organic group.

When the substituent is an alkyl group, the number of carbon atoms is preferably from 1 to 20, and more preferably from 1 to 6 carbon atoms. When the substituent is an alkyl group, it may be a straight chain or branched chain. Specific examples of the substituent group as the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- , n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n- Decyl group and isodecyl group. When the substituent is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When the substituent is an alkoxyl group, the number of carbon atoms is preferably from 1 to 20, and more preferably from 1 to 6 carbon atoms. When the substituent is an alkoxyl group, it may be a straight chain or branched chain. Specific examples of the substituent group of the alkoxyl group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec- , n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group and isodecyloxy group. When the substituent is an alkoxyl group, the alkoxyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxyl group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propoxyoxyethoxyethoxy group, and a methoxy Propyloxy group and the like.

When the substituent is a cycloalkyl group or a cycloalkoxyl group, the number of carbon atoms is preferably from 3 to 10, and more preferably from 3 to 6 carbon atoms. Concrete examples of the substituent group as the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Concrete examples of the substituent in the case where the substituent is a cycloalkoxyl group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group and a cyclooctyloxy group.

When the substituent is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably from 2 to 20, and more preferably from 2 to 7 carbon atoms. Specific examples of the substituent group when the substituent is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group, heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, Pentadecanoyl group, and n-hexadecanoyl group. Specific examples of the substituent group when it is a saturated aliphatic acyloxy group include an acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, N-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n -Tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

When the substituent is an alkoxycarbonyl group, the number of carbon atoms is preferably from 2 to 20, and more preferably from 2 to 7 carbon atoms. Concrete examples of the substituent group of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec- Sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec An octyloxycarbonyl group, a tert-octyloxycarbonyl group, an n-nonyloxycarbonyl group, an isononyloxycarbonyl group, a n-decyloxycarbonyl group and an isodecyloxycarbonyl group.

When the substituent is a phenylalkyl group which may have a substituent, the number of carbon atoms is preferably 7 to 20, and more preferably 7 to 10 carbon atoms. When the substituent is a naphthylalkyl group which may have a substituent, the number of carbon atoms is preferably from 11 to 20, and more preferably from 11 to 14 carbon atoms. Specific examples of the phenylalkyl group in which the substituent 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 naphthylalkyl group in which the substituent may have a substituent include an? -Naphthylmethyl group,? -Naphthylmethyl group, 2- (? -Naphthyl) ethyl group and 2- (? -Naphthyl) .

When the substituent is a heterocyclyl group which may have a substituent, the heterocyclyl group may be a 5-membered or 6-membered ring containing 1 or more N, S, or O, A heterocyclyl group. When the heterocyclyl group is a condensed ring, the number of rings is 3. The heterocycle constituting the heterocyclyl group may be furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, Benzoimidazole, benzothiazole, benzooxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, isoindoline, quinazoline, Phthalazine, cinnoline and quinoxaline.

When the substituent is an amino group substituted with one or two organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, A phenyl group which may have a substituent, a phenylalkyl group which may have a substituent and a carbon number of 7 to 20, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a carbon which may have a substituent A naphthylalkyl group and a heterocyclyl group having a number of 11 to 20, and the like. Specific examples of these preferred organic groups are the same as those exemplified above for the substituent. Specific examples of the amino group substituted with one or two organic groups include a methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di- An amino group, an amino group, an n-pentylamino group, an n-hexylamino group, an n-heptylamino group, an n-octylamino group, N-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, .

Examples of the substituent when the phenyl group, the naphthyl group and the heterocyclyl group in the above substituents have a further substituent include an alkyl group having 1 to 6 carbon atoms; An alkoxyl group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; A phenyl group; Naphthyl group; Benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; A morpholin-1-yl group; Piperazin-1-yl group; A halogen atom; A nitro group; And cyano group. When the phenyl group, the naphthyl group and the heterocyclyl group contained in the above substituent group further have a substituent group, the number of the substituent group is not limited within the range not impairing the object of the present invention, but is preferably 1 to 4. When the phenyl group, the naphthyl group and the heterocyclyl group have a plurality of substituents, the plurality of 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 includes, for example, a phenyl group which may have a substituent. The heteroaryl group which may have a substituent includes, for example, a carbazolyl group which may have a substituent.

In R ² , the substituent which the aryl group, heteroaryl group, phenyl group or carbazolyl group may have is not particularly limited within the range not hindering the object of the present invention. Examples of preferred substituents which the aryl group, heteroaryl group, phenyl group or carbazolyl group may have on the carbon atom include an alkyl group, an alkoxyl group, a cycloalkyl group, a cycloalkoxyl group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, A phenoxy group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl which may have a substituent, a benzoyloxy group which may have a substituent, A phenyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, A naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, a heterocyclic group which may have a substituent Amino group substituted with one or two organic groups of amino group, morpholin-1-yl group, piperazin-1-yl group, halogen atom, nitro group and cyano group.

When R ² is a heteroaryl group or a carbazolyl group, preferred substituents that the heteroaryl group may have on a hetero atom such as a nitrogen atom and examples of preferable substituents that the carbazolyl group may have on the nitrogen atom include alkyl groups, cycloalkyl groups, An aliphatic acyl group, an alkoxycarbonyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, A naphthoyl group which may have a substituent, a naphthylcarbonyl group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl which may have a substituent, and a heterocyclylcarbonyl which may have a substituent. Among these substituents, an alkyl group is preferable, an alkyl group having 1 to 20 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent which the aryl group, heteroaryl group, phenyl group or carbazolyl group may have include an alkyl group, an alkoxyl group, a cycloalkyl group, a cycloalkoxyl group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, A phenylalkyl group which may be substituted, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent and an amino group substituted with one or two organic groups are the same as those described for R ¹ .

When the phenyl group, the naphthyl group and the heterocyclyl group in the above substituents have a further substituent, the substituent is similar to that described for R ¹ .

R ² is preferably a group represented by the following formula (2) or (3) in view of excellent sensitivity of the photosensitive resin composition, more preferably a group represented by the following formula (2) A group represented by A is particularly preferable.

(Wherein R ⁴ is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen atom, a nitro group and a cyano group, 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)

In the case of forming a pattern using the photosensitive resin composition, the pattern tends to be colored by heating in a post bake process at the time of pattern formation. However, when the oxime ester compound represented by the formula (1) wherein R ² is a group represented by the formula (2) and A is a group S is used as a photopolymerization initiator in the photosensitive resin composition, the patterning by heating is suppressed can do.

When R ⁴ in the formula (2) is an organic group, it can be selected from a variety of organic groups to the extent that the object of the present invention is not impaired. In the formula (2), when R ⁴ is an organic group, preferred examples thereof include an alkyl group having 1 to 6 carbon atoms; An alkoxyl group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; A phenyl group; Naphthyl group; Benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; A morpholin-1-yl group; Piperazin-1-yl group; halogen; A nitro group; And cyano group.

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

In the formula (2), n is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. when n is 1, where the combination R ⁴ is preferably in the para position relative to the bonding hands binding with the atoms A is a phenyl group which R ⁴ bonds.

In the formula (3), R &lt; ⁵ &gt; can be selected from a variety of organic groups within the range not impairing the object of the present invention. Preferable examples of R ⁵ include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, A phenoxycarbonyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, A naphthyloxycarbonyl group which may have a substituent, a naphthylalkyl group of 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

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

In the formula (3), R ⁶ is not particularly limited within the range not impairing the object of the present invention, and can be selected from a variety of organic groups. Specific examples of the group represented by 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 heterocyclyl group which may have a substituent. As R ⁶ , among these groups, a phenyl group which may have a substituent is more preferable, and a 2-methylphenyl group is particularly preferable.

When the phenyl group, naphthyl group and heterocyclyl group contained in R ⁴ , R ⁵ or R ⁶ have further substituents, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, A saturated aliphatic acyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, A morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group and a cyano group. When the phenyl group, the naphthyl group and the heterocyclyl group contained in R ⁴ , R ⁵ or R ⁶ further have a substituent, the number of the substituent is not limited to the range not hindering the object of the present invention, Do. When the phenyl group, naphthyl group and heterocyclyl group contained in R ⁴ , R ⁵ or R ⁶ have a plurality of substituents, the plurality of substituents may be the same or different.

In 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 preferable, and a methyl group is more preferable.

The oxime ester compound represented by the general formula (1) can be synthesized, for example, according to the following synthetic scheme. Specifically, a ketone compound represented by the following general formula (2-1) is reacted with a nitrite ester represented by the following general formula (2-2) (RONO, R is an alkyl group having 1 to 6 carbon atoms) in the presence of hydrochloric acid To obtain a ketooxime compound represented by the following general formula (2-3), followed by reacting the ketooxime compound represented by the following general formula (2-3) with an acid anhydride (( R ³ CO) ₂ O) or an acid halide (R ³ COHal, Hal is halogen) represented by the following general formula (2-5) is reacted to obtain an oxime ester compound represented by the following general formula (2-6) have. R ¹ , R ² , R ³ and m in the general formulas (2-1), (2-3), (2-4), (2-5) (1).

<Synthetic Plans>

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

In the pigment dispersion according to the present invention, the content of the oxime ester compound is not particularly limited within the range not hindering the object of the present invention. The content of the oxime ester compound is preferably 1 to 50 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the pigment. The dispersion stability of the pigment in the pigment dispersion obtained by setting the content of the oxime ester compound within this range tends to be good. The pigment dispersion having a content of the oxime ester compound in the above range can be suitably used for preparing a photosensitive resin composition capable of forming a high-adhesion fine pattern with a low exposure dose.

In the pigment dispersion according to the present invention, the total content of the dispersant and the oxime ester compound is preferably 1 to 60 parts by weight, more preferably 1 to 55 parts by weight, and more preferably 1 to 20 parts by weight, By weight is more preferable. When the total content is within the above range, uniform dispersion of the pigment in the pigment dispersion according to the present invention and effect of the oxime ester compound are ensured, and in the pigment dispersion and the photosensitive resin composition obtained from the pigment dispersion, The balance tends to be good. Further, as the upper limit is smaller, the blending amount of the other components in the photosensitive resin composition can be relatively increased, which makes it easier to improve other properties such as sensitivity.

[solvent]

Examples of the solvent in the pigment dispersion according to the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol 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, Ethyl 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 (Poly) alkylene glycol monoalkyl ethers; (Poly) alkylene ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, Methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n- Butyl acetate, isobutyl acetate, isopentyl acetate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, Other esters such as methyl, ethyl acetoacetate and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; Amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetoamide. Solvents may be used alone or in combination of two or more.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3- Tooxybutyl acetate is preferred because it exhibits excellent solubility in alkali-soluble resins, photopolymerizable monomers and photopolymerization initiators to be described later, and a compound represented by the formula (1) as well as good dispersibility of the pigment. Propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate is particularly preferable.

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

[Dispersion aid other than oxime ester compound]

The pigment dispersion according to the present invention may contain a dispersing aid other than the oxime ester compound as an optional ingredient. The dispersion auxiliary other than the oxime ester compound is preferably a dispersion aid having a nitrogen-containing ring in view of the stacking property. For example, a pattern having good adhesion to a substrate and good water resistance can be formed by using a photosensitive resin composition described later It is preferable to be a silane coupling agent having a nitrogen-containing aromatic ring. Specific examples of the silane coupling agent having a nitrogen-containing aromatic ring are those represented by the following formula (11).

R ¹¹ _p R ¹² _(3-p) Si-R ¹³ -NH-C (O) -Y-R ¹⁴ -X (11)

(Wherein R ¹¹ is an alkoxyl group, R ¹² is an alkyl 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 alkylene group, X is a nitrogen-containing heteroaryl group which may have a substituent or may be a monocyclic group, the ring bonding with -YR ¹⁴ - in X is a nitrogen- -YR ¹⁴ - is bonded to the carbon atom in the nitrogen-containing six-membered ring.

In the formula (11), R ¹¹ is an alkoxyl group. The number of carbon atoms of the alkoxyl group relative to R ¹¹ is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 or 2 from the viewpoint of reactivity of the silane coupling agent. Specific preferred examples of R ¹¹ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec- n-hexyloxy group. Among these alkoxyl groups, a methoxy group and an ethoxy group are preferable.

The silanol group formed by the hydrolysis of the alkoxyl group R &lt; ¹¹ &gt; is reacted with the surface of the substrate or the like, so that the adhesion of the pattern formed by using the photosensitive resin composition described later to the substrate surface is improved. Therefore, it is preferable that p is 3 in order to improve the adhesion of the pattern to the substrate surface.

In the formula (11), R ¹² is an alkyl group. The number of carbon atoms of the alkyl group to R ¹² is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 or 2 in view of reactivity of the silane coupling agent. Specific preferred examples of R ¹² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group.

In the formula (11), R ¹³ is an alkylene group. The number of carbon atoms of the alkylene group relative to R ¹³ is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 2 to 4. Specific examples of R ¹³ include methylene, 1,2-ethylene, 1,1-ethylene, propane-1,3-diyl, propane-1,2-diyl, propane- A butane-1, 2-diyl group, a butane-1, 1-diyl group, a butane-1, Diyl group, a butane-2,3-diyl group, a pentane-1,5-diyl group, a pentane-1,4-diyl group and a hexane-1,6-diyl group, , Octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group and dodecane- have. Of these alkylene groups, a 1,2-ethylene group, a propane-1,3-diyl group and a butane-1,4-diyl group are preferable.

Y is preferably -NH-, -O- or -S-, and is preferably -NH-. The bond represented by -CO-NH- is less susceptible to hydrolysis than the bond represented by -CO-O- or -CO-S-, so that in the photosensitive resin composition described later, the silane coupling agent in which Y is -NH- It is easy to form a pattern having excellent water resistance.

R ¹⁴ is a single bond or an alkylene group, preferably a single bond. A preferable example of the case where R ¹⁴ is an alkylene group is the same as R ¹³ .

X is a nitrogen-containing heteroaryl group which may have a substituent or may be a monocyclic or not, and the ring which bonds with -YR ¹⁴ - in X is a nitrogen-containing six-membered ring, and -YR ¹⁴ - And is bonded to a carbon atom in the ring. The reason is unclear, however, when such a silane coupling agent having X in the photosensitive resin composition described later is used, a pattern excellent in adhesiveness to a substrate and water resistance can be formed.

When X is a polycyclic heteroaryl group, the heteroaryl group may be a condensed group of a plurality of monocyclic rings, and a plurality of monocyclic rings may be bonded through a single bond. When X is a polycyclic heteroaryl group, the number of rings included in the polycyclic heteroaryl group is preferably from 1 to 3. When X is a polycyclic heteroaryl group, a ring condensed or bonded to a nitrogen-containing six-way ring in X may or may not contain a heteroatom, and may not be a ring in the direction ring.

Examples of the substituent which X as the nitrogen-containing heteroaryl group may have include an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms A nitro group, a nitro group, an amino group, a hydroxy group, a mercapto group, a cyano group, a sulfonic acid group, a carboxy group and a halogen atom. The number of substituents X has is not particularly limited as long as it does not impair the object of the present invention. The number of substituents of X is preferably 5 or less, more preferably 3 or less. When X has plural substituents, plural substituents may be the same or different.

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

Among these groups, a group represented by the following formula is more preferable as 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 oxime ester compound in the pigment dispersion of the present invention is preferably 0.1 to 10 wt%, more preferably 0.5 to 5 wt%.

[Method for preparing pigment dispersion]

The pigment dispersion according to the present invention is prepared by mixing (dispersing / kneading) a pigment comprising a nitrogen-containing aromatic ring compound, a dispersant, the oxime ester compound and a solvent with a stirrer such as a three-stage roll mill, a ball mill or a sand mill, Therefore, it can be prepared by filtration with a filter such as a 5 占 퐉 membrane filter. In the preparation of the pigment dispersion, a pigment comprising a nitrogen-containing aromatic ring compound and an oxime ester compound (as a dispersing aid) are mixed (dispersed and kneaded) together in a stirrer to prepare a pigment comprising a nitrogen-containing aromatic ring compound and the oxime ester It is believed that the effect of the present invention is obtained because the π-π interaction occurs between the compounds.

<Photosensitive resin composition>

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

[Base resin]

The base resin is not particularly limited, and known resins commonly used in the photosensitive resin composition can be mentioned. The base resin may be used alone or in combination of two or more.

Examples of the base resin include a polymerizable resin such as a polymerizable group-containing resin. Examples of such a polymerizable resin include those having an ethylenic unsaturated group in an alkali-soluble resin described later.

As the base resin, an alkali-soluble resin can be mentioned. When a resin film having a thickness of 1 占 퐉 is formed on a substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by weight and the substrate is immersed in a KOH aqueous solution having a concentration of 0.05% by weight for 1 minute, Means that the thickness is 0.01 占 퐉 or more.

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

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

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

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

In the formula (a-1), Y ^a represents a residue other than 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, methylendomethylene tetrahydrophthalic anhydride, chlorenedic anhydride, methyltetrahydrophthalic anhydride, And glutaric acid.

In the above formula (a-1), Z ^a represents a residue of the tetracarboxylic acid dianhydride excluding two acid anhydride groups. Examples of the tetracarboxylic acid dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride.

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

The weight average molecular weight of the resin having (A1) cardo structure is preferably 1000 to 40000, more preferably 2000 to 30,000. Within the above range, sufficient heat resistance and film strength can be obtained while satisfactory developability is obtained.

Another example of the preferable alkali-soluble resin is (A2) epoxy resin. (A2) The epoxy resin is not particularly limited, and conventionally known epoxy resins can be used, and those having no ethylenic unsaturated group or those having an ethylenic unsaturated group may be used.

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

Examples of the unsaturated carboxylic acid include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, metaconic acid and itaconic acid; Anhydrides of these dicarboxylic acids; And the like. Of these, (meth) acrylic acid and maleic anhydride are preferable from the viewpoint of copolymerization reactivity, alkali solubility of the obtained resin, availability and the like. These unsaturated carboxylic acids may be used alone or in combination of two or more.

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

The proportion of the constituent unit derived from an unsaturated carboxylic acid (constituent unit having a carboxyl group) in the resin (A2-1) is preferably 5 to 29% by weight, more preferably 10 to 25% by weight. Within the above range, the developability of the photosensitive resin composition can be made appropriate.

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

Examples of the epoxy group-containing unsaturated compound having no alicyclic epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) (Meth) acrylic acid epoxy alkyl esters such as heptyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate; ? -alkylacrylic acid epoxyalkyl esters such as glycidyl? -ethyl acrylate, glycidyl? -n-propyl acrylate, glycidyl? -n-butyl acrylate, and 6,7-epoxyheptyl? -ethylacrylate; glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether; And the like. Of these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o-vinyl Benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether are preferred.

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

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

Wherein R ^a3 represents a hydrogen atom or a methyl group, R ^a4 represents a bivalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ^a5 represents a bivalent hydrocarbon group having 1 to 10 carbon atoms, 10 &lt; / RTI &gt; R ^a4 is preferably a linear or branched alkylene group such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, and hexamethylene groups. Examples of R ^a5 include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH ₂ -Ph-CH ₂ - (Ph Represents a phenylene group).

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

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

It is preferable that the resin (A2-1) is further copolymerized with an unsaturated alicyclic group-containing compound.

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

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

Wherein R ^a6 represents a hydrogen atom or a methyl group, R ^a7 represents a single bond or a bivalent aliphatic 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. As R ^a7 , a single bond, a straight chain or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group is preferable. As R ^a8, for example, methyl group and ethyl group are preferable.

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

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

Examples of the (meth) acrylic esters include linear or branched (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate and t- Chain alkyl (meth) acrylates; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono Furfuryl (meth) acrylate; And the like.

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

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caprylate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; Allyloxyethanol; And the like.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2- But are not limited to, ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether Alkyl vinyl ethers such as methyl vinyl ether; Vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether and vinyl anthranyl ether; And the like.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethylacetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinylphenylacetate , Vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl naphthoate.

Examples of the styrenes include styrene; Examples of the monomer include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, , And acetoxymethylstyrene; Alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene, and dimethoxystyrene; But are not limited to, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo- Halostyrenes such as methylstyrene and 4-fluoro-3-trifluoromethylstyrene; And the like.

The weight average molecular weight of the resin (A2-1) is preferably from 2,000 to 50,000, more preferably from 5,000 to 30,000. When the amount is in the above range, there is a tendency to balance the thin film performance and developability of the photosensitive resin composition.

Examples of the epoxy resin having an ethylenic unsaturated group include a resin (A2-2) obtained by reacting a carboxyl group of a resin obtained by at least polymerization of an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound with an epoxy group of an epoxy group-containing unsaturated compound, (A2-3) obtained by reacting an epoxy group of a resin obtained by at least polymerizing a carboxylic acid and an epoxy group-containing unsaturated compound with a carboxyl group of an unsaturated carboxylic acid can be used.

Examples of the unsaturated carboxylic acid and epoxy group-containing unsaturated compound include the compounds exemplified for the resin (A2-1). Accordingly, the resin (A2-1) is exemplified as a resin obtained by at least polymerizing an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound.

The proportion of the unsaturated carboxylic acid-derived constituent unit (constituent unit having a carboxyl group) in the resins (A2-2) and (A2-3) is preferably 5 to 60% by weight, more preferably 10 to 40% Do. Within the above range, the developability of the photosensitive resin composition can be made appropriate.

The proportion of the constituent unit derived from an epoxy group-containing unsaturated compound (constituent unit having an epoxy group) in the resin (A2-2) or (A2-3) is preferably 5 to 90% by weight, more preferably 15 to 75% Is more preferable. By setting the thickness within the above range, it becomes easy to form a color filter or the like having a good shape.

The weight average molecular weights of the resins (A2-2) and (A2-3) are preferably from 2,000 to 50,000, and more preferably from 5,000 to 30,000. When the amount is in the above range, there is a tendency to balance the thin film performance and developability of the photosensitive resin composition.

In addition to the above, (A2) epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol or cresol novolak type epoxy resins, resole type epoxy resins, triphenolmethane type epoxy resins, An epoxy (meth) acrylate resin obtained by reacting an epoxy group of an epoxy resin with (meth) acrylic acid such as polyglycidyl ester of carboxylic acid, polyol polyglycidyl ester, amine epoxy resin and dihydroxybenzene type epoxy resin It is possible.

The content of the base resin is preferably from 40 to 85% by weight, more preferably from 45 to 75% by weight, based on the solid content of the photosensitive resin composition. When the amount is in the above range, balance of developability tends to be easily obtained.

[Photopolymerization initiator]

The photopolymerization initiator is not particularly limited, and conventionally known photopolymerization initiators can be used. The photopolymerization initiator may be used alone 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, 1- [4- (2- hydroxyethoxy) Methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- (4-dimethylaminophenyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4 Dimethylaminobenzoic acid, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-ethylbenzoic acid, benzyl- benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4- 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, Hexanethene, octanethene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, Benzene anthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2- mercaptobenzooxazole, 2- Sol, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- But are not limited to, 4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bismethylaminobenzophenone Ketone), 4,4'-bisdiethylaminobenzophenone (i.e., ethylmihaler ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone , p-dimethyl acetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyl acetophenone, p-dimethylaminoacetophenone, p-tert- butyltrichloroacetophenone, p -tetra-butyl dichloroacetophenone,?,? -dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) heptane, Tri (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine , 2- [2- (5-methylfuran-2- (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis Triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis Bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl- 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4- Methoxy) styrylphenyl-s-triazine, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- 3-yl], 1- (O-acetyloxime), 1,2- Benzyloxime), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, "NCI-831" : Manufactured by ADEKA). The oxime ester compound used in the present invention, that is, an oxime ester compound having an aromatic ring or an aromatic heterocyclic ring bonded through an organic group containing a ring ring to a carbon atom contained in the oxime group and a carbonyl group can also be used as a photopolymerization initiator . That is, in the photosensitive resin composition according to the present invention, the oxime ester compound is included as a dispersing aid (included as a dispersing aid in the pigment dispersion), but may also be contained as a photopolymerization initiator. In this case, it is considered that the oxime ester compound as a photopolymerization initiator does not cause a pi-pi interaction with the pigment comprising the nitrogen-containing cyclic compound. The oxime ester compound as a photopolymerization initiator is the same as described above, and the compound represented by the above formula (1) is preferable.

The content of the photopolymerization initiator is preferably 0.5 to 20% by weight based on the solid content of the photosensitive resin composition. Within the above range, sufficient heat resistance and chemical resistance can be obtained, and the coating film forming ability can be improved and the hardening failure can be suppressed.

When the photosensitive resin composition contains the oxime ester compound as a photopolymerization initiator, the proportion of the oxime ester compound is preferably 1 to 100% by weight, more preferably 20 to 100% by weight, based on the total amount of the photopolymerization initiator By weight, more preferably 50 to 100% by weight, and particularly preferably 80 to 100% by weight. The sensitivity and the fine line adhesion of the photosensitive resin composition can be improved by setting the amount in the above range.

[Pigment dispersion]

The content of the pigment dispersion according to the present invention may be appropriately determined depending on the use of the photosensitive resin composition. For example, the content of the pigment in the photosensitive resin composition is preferably 5 to 70% by weight based on the solid content of the photosensitive resin composition, More preferably from 25 to 60% by weight.

When the photopolymerizable monomer to be described later is used, the content of the pigment dispersion according to the present invention is preferably such that the content of the oxime ester compound in the photosensitive resin composition is 0.01 to 2.5 wt% based on 100 parts by weight of the total amount of the base resin and the photopolymerizable monomer The amount added is preferably 0.01 to 0.5 parts by weight, more preferably. By adjusting the content of the pigment dispersion according to the present invention so that the content of the oxime ester compound in the photosensitive resin composition is within this range, it becomes easy to form a fine pattern having excellent adhesion to the substrate.

[Photopolymerizable Monomer]

The photosensitive resin composition according to the present invention may contain a photopolymerizable monomer. The photopolymerizable monomer is not particularly limited, and conventionally known monofunctional monomers and multifunctional monomers can be used. The photopolymerizable monomers may be used alone or in combination of two or more.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxy Acrylates such as methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic anhydride, itaconic acid, (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl acrylate, Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl Acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, (Meth) acrylates such as 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (Meth) acrylate of 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate and phthalic acid derivatives . These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, butyleneglycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol (Meth) acrylate, 2,2-bis (4- (meth) acryloxy diethoxyphenyl) propane, (Meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl (Meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene di A reaction product of isocyanate and 2-hydroxyethyl (meth) acrylate, a condensate of methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, polyhydric alcohol and N-methylol Monomer And triacryl acrylamide. These polyfunctional monomers may be used alone or in combination of two or more.

The content of the photopolymerizable monomer is preferably 1 to 30% by weight, more preferably 5 to 20% by weight, based on the solid content of the photosensitive resin composition. When the concentration is in the above range, balance of sensitivity, developability and resolution tends to be easily obtained.

[Other ingredients]

The photosensitive resin composition may contain various additives as required. Examples of the additives include a sensitizer, a hardening accelerator, a filler, an adhesion promoter, an antioxidant, an anti-aggregation agent, a thermal polymerization inhibitor, a defoaming agent, and a surfactant.

&Lt; Method of producing photosensitive resin composition >

The method for producing a photosensitive resin composition according to the present invention includes at least a step of mixing a base resin, a photopolymerization initiator and a pigment dispersion according to the present invention. In this step, the photopolymerizable monomer and / or other components may be mixed in addition to the above components. These components can be mixed by a stirrer such as a three-stage roll mill, a ball mill, a sand mill or the like. Further, the photosensitive resin composition may be filtered using a filter such as a 5 占 퐉 membrane filter so as to make the prepared photosensitive resin composition uniform.

In the method for producing a photosensitive resin composition according to the present invention, a pigment dispersion is prepared by premixing a pigment comprising a nitrogen-containing cyclic compound, a dispersant, the oxime ester compound, and a solvent in advance to prepare a pigment dispersion, . By such a process, a photosensitive resin composition capable of forming a high-adhesion small pattern even at a low exposure dose can be obtained.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these examples.

In the following Examples and Comparative Examples, the following Compound 1 and Comparative Compounds 1 to 4 were used as oxime ester compounds.

&Lt; Synthesis of oxime ester compound >

Hereinafter, the synthesis of Compound 1 will be described with reference to Synthesis Example 1.

[Synthesis Example 1]

(23.13 mmol) of 2- (2-methylphenyl) -1- [4- (phenylsulfanyl) phenyl] ethane-1,2-dione and 2.93 g (42.16 mmol) of hydroxylamine hydrochloride and 4.15 g (41.01 mmol) were mixed with 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, and the mixture was washed with saturated brine, dried over anhydrous magnesium sulfate and evaporated to give 2- (2-methylphenyl) 2- (N-hydroxyimino) -1- [4- ) Phenyl] ethan-1-one. To 8.03 g of the obtained 2- (2-methylphenyl) -2- (N-hydroxyimino) -1- [4- (phenylsulfanyl) phenyl] ethan- 1-one was dissolved in acetic anhydride 13.33 g (130.57 mmol) Acetylation to obtain 6.25 g of the oxime ester compound represented by the above formula.

&Lt; Preparation of pigment dispersion >

[Examples 1 to 10 and Comparative Examples 1 to 10]

A pigment, a dispersant and an oxime compound shown in Table 1 were mixed and dissolved in a solvent shown in Table 1 to prepare a pigment dispersion having a solid content concentration of 17 to 23 wt%. The amount of each component used is shown in Table 1. Details of the pigment, the dispersant and the solvent are as follows. Mixture 1 of Example 10 is a mixture (weight ratio 1: 1) of the compound 1 (oxime ester compound) synthesized above and a silane coupling agent having a nitrogen-containing aromatic ring represented by the following formula.

· Pigment

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

B15: 6 (C.I. Pigment Blue 15: 6, phthalocyanine pigment represented by the following formula)

G58 (C.I. Pigment Green 58, a phthalocyanine pigment represented by the rightmost formula below)

Perylene (3,4,9,10-perylene tetracarboxydiamide: R ^e7 and R ^{e8 in} the formula (e-3) are hydrogen atoms)

· Dispersant

Acrylic resin-based polymeric dispersing agent (trade name: Disper BYK2001, manufactured by BICKEMISA)

·solvent

3-methoxybutyl acetate / propylene glycol monomethyl ether acetate = 60/40 (weight ratio) mixed solvent

[Evaluation of viscosity]

The viscosity of the pigment dispersion immediately after preparation was measured using an E-type viscometer (manufactured by Tokyo Instruments Co., Ltd.). Further, the pigment dispersion was filled in a light-shielding glass container and allowed to stand in a closed state at 40 DEG C for 7 days, and then the viscosity of the pigment dispersion was once again measured using an E-type viscometer. When the difference between the viscosity immediately after the preparation and the value of the viscosity after standing at 40 캜 for 7 days is 0.3 mPa s or less, it is determined that the dispersion stability of the pigment dispersion is good (∘). If the difference exceeds 0.3 mPa · s , And that the dispersion stability of the pigment dispersion was poor (x). The results are shown in Table 1.

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

&Lt; Preparation of Photosensitive Resin Composition >

[Examples 11 to 24 and Comparative Examples 11 to 21]

20 parts by weight of the photopolymerization initiator shown in Table 2, 30 parts by weight of resin A (solid content: 55% by weight, solvent: 3-methoxybutyl acetate), 30 parts by weight of dipentaerythritol hexaacrylate and the pigment dispersion (60% by weight) and propylene glycol monomethyl ether acetate (40% by weight) were added to 100 parts by weight of a pigment dispersion having a solid content of 17 to 23% by weight and a pigment content of 15% Were mixed and then filtered through a membrane filter having a diameter of 5 탆 to prepare a photosensitive resin composition. Further, the amount of the mixed solvent was adjusted to adjust the solid content concentration in the photosensitive resin composition to 15% by weight.

Details of "OXE01" and "Compound 1 + OXE01" in the photopolymerization initiator shown in Table 2 are as follows.

OXE01: a photopolymerization initiator (trade name: IRGACURE OXE01: 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)])

Compound 1 + OXE01: A mixture of Compound 1 and OXE01 (weight ratio 1: 1)

The resin A used for the preparation of the photosensitive resin composition was the one synthesized in accordance with the following prescription.

First, 235 g of a bisphenol fluorene epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol and 72.0 g of acrylic acid were added to a 500 ml four- At a rate of 25 ml / min while blowing air thereinto. Subsequently, the solution was gradually heated up to a cloudy state and heated at 120 DEG C to be completely dissolved. At this time, the solution was gradually turned transparent, but stirring was continued. The acid value was measured therebetween, and heating and stirring were continued until the concentration was less than 1.0 mg KOH / g. 12 hours were required until the acid value reached the target value. The mixture was then cooled to room temperature to obtain a bisphenol fluorene-type epoxy acrylate represented by the following structural formula (a-4) as a colorless transparent solid.

Subsequently, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene type epoxy acrylate thus obtained, and then 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually heated The reaction was carried out at 110 to 115 ° C for 4 hours. After disappearance of the acid anhydride group was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to obtain a resin A. The disappearance of the acid anhydride was confirmed by IR spectrum. This resin A corresponds to the compound represented by the aforementioned general formula (a-1).

Each of the photosensitive resin compositions of Examples 11 to 24 and Comparative Examples 11 to 21 was evaluated for coloring by post-baking and evaluation of thin wire adhesion by the following method. The results are shown in Table 2.

[Evaluation of coloring]

Coloring evaluation was carried out for each of the photosensitive resin compositions of Examples 11 to 24 and Comparative Examples 11 to 21 in the following procedure.

First, the photosensitive resin composition was spin-coated on a glass substrate (10 cm x 10 cm) and heated at 90 占 폚 for 120 seconds to form a 1.0 占 퐉 coating film on the surface of the glass substrate. Thereafter, the coating film was exposed using a Miller Projection aligner (product name: TME-150RTO, manufactured by Topcon Corporation) at an exposure dose of 20, 50, 100 or 200 mJ / cm ² and an exposure gap of 200 탆. The exposed film was developed in a 0.04% by weight aqueous solution of KOH at 26 DEG C for 30 to 50 seconds, and post-baked at 230 DEG C for 30 minutes. The coating film before and after the post-baking was measured by using an instantaneous multi-photometry system (MCPD-3000: manufactured by Otsuka Electronics Co., Ltd.) with a difference in transmittance in the wavelength region of 380 nm to 780 nm as? Y. The values of? Y are shown in Table 2. The smaller the absolute value of? Y, the less the coloration.

[Evaluation of fine wire adhesion]

The photosensitive resin compositions of Examples 11 to 24 and Comparative Examples 11 to 21 were coated on a glass substrate (100 mm x 100 mm) using a spin coater and prebaked at 90 캜 for 120 seconds to form a coating film having a thickness of 1.0 탆 . Subsequently, the coating film was irradiated with ultraviolet rays through a negative mask in which a line pattern of 5 mu m was formed with an exposure gap of 50 mu m using a Miller projection aligner (trade name: TME-150RTO, manufactured by Topcon Corporation). The exposure was carried out in four steps of 20, 50, 100 and 200 mJ / cm ² . After the exposure, the coated film was developed with a 0.04% by weight KOH aqueous solution at 26 DEG C for 40 seconds and post-baked at 230 DEG C for 30 minutes to form a line pattern.

The formed line pattern was observed by an optical microscope and the fine line adhesion was evaluated. The fine line adhesion was evaluated as &quot; good &quot; when the line pattern was not peeled from the substrate, and &quot; poor &quot; when the line pattern was not peeled off from the substrate. The results are shown in Table 2.

As can be seen from Table 2, in Examples 11 to 24, coloring due to heating at the time of post-baking can be suppressed, and a line pattern of 5 m was adhered to the substrate at an exposure amount of 50 mJ / cm ² . Particularly, in Examples 12 to 15 and 17 to 24, even a low exposure dose of 20 mJ / cm &lt; ² &gt;

In contrast, in Comparative Examples 11, 14, 15, and 17, coloring due to heating at the time of post-baking could be suppressed, but at an exposure amount of 50 mJ / cm ² , a line pattern of 5 탆 was not adhered to the substrate. Compared with Examples 11 to 24, the fine wire adhesion was poor.

In Comparative Example 12, 13, 20 and 21 in the line pattern of the 5㎛ close contact with the substrate at the exposure amount, called 50mJ / cm ² and, in particular, in Comparative Examples 12, 20 and 21, even in low exposure amount, called 20mJ / cm ² A line pattern of 5 mu m adhered to the substrate. However, in Comparative Examples 12, 13, 20 and 21, coloration due to heating during post-baking could not be suppressed. Although the photosensitive resin composition of Comparative Examples 12 and 13 contains Compound 1 as a photopolymerization initiator, it can not be inhibited in coloration, and therefore it is considered that the π-π interaction does not occur between the pigment composed of the compound 1 and the nitrogen ring- do.

Further, in Comparative Examples 16, 18, and 19, coloring due to heating at the time of post-baking can not be suppressed. Further, at an exposure amount of 50 mJ / cm ² , line patterns of 5 탆 do not adhere to the substrate, 24, the adhesion of the fine wires was poor.

Claims (6)

Wherein the oxime ester compound comprises an organic group containing a ring in the carbon atom contained in the oxime group and an organic group containing an aromatic ring or an aromatic hydrocarbon ring through a carbonyl group, Wherein the aromatic heterocycle is bonded. The method 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 a heteroaryl group which may have a substituent or an aryl group which may have a substituent, R ³ is a hydrogen atom or an alkyl group of carbon number 1 to 6 . The method of claim 2,
Wherein R &lt; ² &gt; is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent. 1. A photosensitive resin composition comprising a base resin, a photopolymerization initiator, and the pigment dispersion according to claim 1. Wherein the oxime ester compound is an oxime ester compound in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is bonded through an organic group containing an aromatic ring to a carbon atom contained in an oxime group through a carbonyl group. The method of 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 a heteroaryl group which may have a substituent or an aryl group which may have a substituent, R ³ is a hydrogen atom or an alkyl group of carbon number 1 to 6 .