KR102546435B1 - Pigment dispersion, photosensitive resin composition therewith, and dispersion aids - Google Patents

Abstract

[Problem] To provide a colorant dispersion capable of providing a photosensitive resin composition capable of forming a highly adherent micropattern even at a low exposure amount, with good dispersion stability of the colorant even when the content of the dispersant is reduced, a photosensitive resin composition containing the same, and a dispersion aid do.
[Solution] The colorant dispersion according to the present invention contains a colorant, a dispersant, an oxime compound represented by Formula (1), and a solvent. In the formula, R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, R ² and R ³ are each a chain alkyl group, a cyclic hydrocarbon group or a heteroaryl group, and R ² and R ³ may combine with each other to form a spiro ring. R ⁴ is a monovalent organic group, R ⁵ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and m is 0 or 1. The photosensitive resin composition according to the present invention contains a base resin, a photopolymerization initiator, and the colorant dispersion. The dispersion aid according to the present invention consists of the above oxime compound.

Description

Colorant dispersion, photosensitive resin composition containing the same, and dispersing aid

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

The liquid crystal panel includes a black matrix for enhancing the contrast of an image and a color filter on which an RGB color layer generally composed of red (R), green (G), and blue (B) is formed. These black matrices and color filters are formed by repeatedly applying a photosensitive resin composition in which a black or colorant of each color is dispersed to a substrate, drying, exposing and developing the obtained coating film, and forming a desired pattern. In order to prepare such a photosensitive resin composition, a colorant dispersion in which a colorant is dispersed is used. For example, Patent Document 1 discloses a pigment dispersion containing a pigment, a solvent, a dispersant, and a specific additive having an azo group, an amide group, and a carbonyl group.

Japanese Unexamined Patent Publication No. 2012-087233

In recent years, technological innovation has progressed in higher resolution of liquid crystal panels, and improvement in color development of RGB colored layers has been required. By increasing the concentration of the coloring agent in the photosensitive resin composition for providing the RGB colored layer, the color developing property can be improved. However, since a high concentration of the coloring agent causes a decrease in the sensitivity of the photosensitive resin composition to light, it is difficult to form a pattern of a good shape with a low exposure amount, and productivity in the exposure step tends to decrease.

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

The present invention has been made in view of such a conventional situation, and a colorant dispersion solution capable of providing a photosensitive resin composition capable of forming a highly adherent micropattern even at a low light exposure amount and having good dispersion stability of the colorant even when the content of the dispersant is reduced. It aims at providing the containing photosensitive resin composition, and a dispersing aid.

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

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

[Tue 1]

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

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

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

According to the present invention, even if the content of the dispersant is reduced, the dispersion stability of the colorant is good, and a colorant dispersion capable of providing a photosensitive resin composition capable of forming a highly adherent micropattern even at a low exposure amount, a photosensitive resin composition containing the same, and a dispersion aid can provide.

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

[coloring agent]

The colorant dispersion liquid according to the present invention contains a colorant. By containing such a colorant, the colorant dispersion liquid according to the present invention is suitably used for formation of, for example, color filters, paints, solder resists, and inkjet inks for liquid crystal displays. In addition, the colorant dispersion according to the present invention contains a light-shielding agent as a colorant, and is therefore preferably used for forming a black matrix in a color filter of a display device, for example. The above colorants can be used alone or in combination of two or more.

The colorant contained in the colorant dispersion according to the present invention is not particularly limited, but a pigment or dye can be used. For example, it is classified as a pigment in the color index (C.I.; published by The Society of Dyers and Colourists). It is preferable to use a compound with a color index (C.I.) number as shown below.

Examples of yellow pigments that can be suitably used include C.I. Pigment Yellow 1 (hereinafter, “C.I. 31,53, 55, 60, 61,65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 1 68, 175, 180, and 185.

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

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

Examples of red pigments that can be suitably used include C.I. Pigment Red 1 (hereinafter, "C.I. Pigment Red" is the same and only numbers are written) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18 , 19, 21,22, 23, 30, 31,32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50 :1,52:1,53:1,57, 57:1,57:2, 58:2, 58:4,60:1,63:1,63:2, 64:1, 81:1, 83 , 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171 ; 223 , 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265, 270, and 272.

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

Examples of pigments of other colors described above that can be suitably used include C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Green pigments such as Pigment Green 58, C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Brown pigments such as Pigment Brown 28, C.I. Black pigments, such as pigment black 1 (hereinafter "C.I. pigment black" is the same and only a number is described), 7, 30, 31, 32, 33, 34, etc. are mentioned.

Moreover, when using a colorant as a light-shielding agent, it is preferable to use a black pigment as a light-shielding agent. As the black pigment, carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, metal oxides, composite oxides, metal sulfides, metal sulfates, or metal carbonates such as silver, organic substances and inorganic substances, etc. Various pigments are mentioned. Among these, it is preferable to use carbon black having high light-shielding properties.

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

Since resin-coated carbon black has lower conductivity than carbon black without resin coating, when used as a black matrix for a liquid crystal display element such as a liquid crystal display, leakage of current is small and a highly reliable display with low power consumption can be produced. can do.

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

The inorganic pigment and the organic pigment may be used individually or in combination of two or more, respectively, but when used together, it is preferable to use the organic pigment in the range of 10 to 80 parts by weight with respect to 100 parts by weight of the total amount of the inorganic pigment and the organic pigment. It is more preferable to use in the range of 40 parts by weight.

In addition, the colorant contained in the colorant dispersion according to the present invention may be a pigment composed of a nitrogen-containing aromatic ring compound. Although it does not specifically limit as a pigment which consists of a nitrogen-containing aromatic ring compound, For example, diketopyrroropyrrole pigment, phthalocyanine pigment, perylene pigment, azo pigment, quinacridone pigment, benzimidazolone pigment, iso Indolinone-based pigments, dioxazine-based pigments, indanthrene-based pigments, and the like are exemplified, and diketopyrrolopyrrole-based pigments, phthalocyanine-based pigments, and/or perylene-based pigments are preferably used.

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

[Tue 2]

In formula (b-1), A3 and A4 each independently represent a halogen atom, a methyl group, an ethyl group, a tert-butyl group, a phenyl group, a N,N-dimethylamino group, a trifluoromethyl group, and a cyano group, and k and k' Each independently represents an integer from 0 to 5, and when k and k' are each an integer of 2 or more, a plurality of A3 and A4 may be the same or different, respectively.)

In 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, and k and k' are each independently 0 from the viewpoint of achieving high contrast and making it easy to adjust red suitable for a color filter or the like. Or it is more preferably an integer of 1.

As diketopyrrolopyrrole pigments, among others, C.I. 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 preferred, and in terms of color and tinting power, C.I. Pigment Red 254, C.I. It is more preferable that it is Pigment Red 255. Diketopyrroropyrrole pigments can be used alone or in combination of two or more.

The average primary particle diameter of the diketopyrrolopyrrole pigment used in the present invention is not particularly limited as long as it is possible to develop a desired color. From the point of improving contrast, it is preferable that it exists in the range of 10-50 nm, and it is more preferable that it exists in the range of 10-30 nm. By setting the average primary particle size of the pigment within the above range, for example, a color filter with high contrast and high quality can be obtained. In addition, the average particle diameter of the pigment can be obtained by directly measuring the size of primary particles from electron micrographs. Specifically, the minor axis diameter and the major axis diameter of each primary particle are measured, and the average is taken as the particle diameter of the particle. Next, for 100 or more particles, the volume (mass) of each particle is approximated with a rectangular parallelepiped of the obtained particle diameter to obtain a volume average particle diameter, which is taken as the average particle diameter. In addition, the same result can be obtained even if either a transmission type (TEM) or a scanning type (SEM) is used as an electron microscope.

The diketopyrroropyrrole pigment used in the present invention can be prepared by a known method such as a recrystallization method or a solvent salt milling method. Moreover, you may use a commercially available diketopyrrolopyrrole pigment.

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

[Tue 3]

[In the formula, X ₁ to X ₄ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, a substituent which may have An alkoxyl group, 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 are shown. 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 from 0 to 4, and m1+n1, m2+n2, m3+n3, and m4+n4 each represent an integer from 0 to 4. , and 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 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, and a substituent. A heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, and an arylthio group which may have a substituent are exemplified. When the above X ₁ to X ₄ have a substituent, the substituent may be the same or different, and specific examples include halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms, characteristic groups such as amino groups, hydroxyl groups, and nitro groups, as well as alkyl groups , an aryl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, and the like. Moreover, there may be many of these substituents.

As the "alkyl group" of the alkyl group which may have a substituent, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group, stearyl group, straight-chain or branched alkyl groups such as 2-ethylhexyl group, and examples of the "alkyl group having a substituent" include trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-di Bromoethyl group, 2,2,3,3-tetrafluoropropyl group, 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, etc. are mentioned.

Examples of the "aryl group" of the aryl group which may have a substituent include a phenyl group, a naphthyl group, an anthryl group, and the like, and examples of the "aryl group having a substituent" include p-methylphenyl group, p-bromophenyl group, and p-nitrophenyl group , p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group A tyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, a 2-amino anthraquinonyl group, etc. are mentioned.

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, and examples of the “cycloalkyl group having a substituent” include a 2,5-dimethylcyclopentyl group, 4-tert - A butylcyclohexyl group etc. are mentioned.

Examples of the "heterocyclic group" of the heterocyclic group which may have a substituent include a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, and an acridinyl group, and the "heterocyclic group having a substituent" 3-methylpyridyl group, N-methylpiperidyl group, N-methylpyrrolyl group, etc. are mentioned.

As the "alkoxyl group" of the alkoxyl group which may have a substituent, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2,3 -Dimethyl-3-pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, etc. straight-chain or branched alkoxyl groups are exemplified, and "alkoxyl group having a substituent" As trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxyl group, 2,2-ditrifluoromethylpropoxyl group A oxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group, etc. are mentioned.

Examples of the "aryloxy group" of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, and anthryloxy group, and examples of the "aryloxy group having a substituent" include p-methylphenoxy group and p-nitro A phenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group, etc. are mentioned.

As the "alkylthio group" of the alkylthio group which may have a substituent, methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group , octadecylthio group, etc., and "alkylthio group having a substituent" include methoxyethylthio group, aminoethylthio group, benzylaminoethylthio group, methylcarbonylaminoethylthio group, phenylcarbonylaminoethyl Thioggi etc. are mentioned.

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

Next, as specific examples of Y ₁ to Y ₄ , a halogen atom, a nitro group, a phthalimidemethyl group which may have a substituent (C ₆ H ₄ (CO) ₂ N-CH ₂ -), a sulfamoyl group (H ₂ NSO ₂ -) can be heard. A phthalimidemethyl group having a substituent represents a structure in which hydrogen atoms in a phthalimidemethyl group are substituted by a substituent, and a sulfamoyl group having a substituent represents a structure in which hydrogen atoms in a sulfamoyl group are substituted by a substituent. Preferred Y ₁ to Y ₄ are a halogen atom and a sulfamoyl group. A phthalocyanine compound in which m1 to m4 is 0 (ie, Y ₁ to Y ₄ is absent) can also be suitably used. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. The “substituent” of the phthalimidemethyl group which may have a substituent and the sulfamoyl group which may have a substituent is synonymous with the substituents of X ₁ to X ₄ .

As a phthalocyanine pigment, 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, etc.) is preferred, 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 are more preferred. A phthalocyanine-type pigment can be used individually by 1 type or in combination of 2 or more types.

The phthalocyanine-based pigment used in the present invention can be prepared by a known method. Moreover, you may use a commercially available phthalocyanine type pigment.

Examples of the perylene pigment include a perylene pigment represented by the following formula (e-1), a perylene pigment represented by the following formula (e-2), and a perylene pigment represented by the following formula (e-3). Commercially available products include BASF's product names K0084 and K0086, and C.I. Pigment Black 21 (hereinafter "C.I. Pigment Black" is the same and only numbers are described), 30, 31, 32, 33, 34, etc. can be preferably used as the perylene pigment.

[Tuesday 4]

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

[Tuesday 5]

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

[Tue 6]

In formula (e-3), R ^e7 and R ^e8 are each independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and may contain N, O, S, or P hetero atoms. When ^Re7 and ^Re8 are alkyl groups, the alkyl group may be linear or branched.

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) are, for example, Japanese Patent Application Publication No. 62-1753, Japanese Patent Publication No. 63- It can be synthesized using a method described in Publication No. 26784 or the like. That is, perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines are used as raw materials, and a heating reaction is performed in water or an organic solvent. Then, the desired product can be obtained by reprecipitating the obtained preparation in sulfuric acid or by recrystallizing it in water, an organic solvent, or a mixed solvent thereof.

In order to favorably disperse the perylene-based pigment, it is preferable that the average particle diameter of the perylene-based pigment is 10 to 1000 nm.

The content of the colorant is preferably 5 to 95% by weight, more preferably 25 to 90% by weight, based on the solid content of the colorant dispersion according to the present invention.

[Dispersant]

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

As the dispersing agent, known ones can be mentioned, and it is preferable to use a polyethyleneimine-based polymer dispersing agent, a urethane resin-based polymer dispersing agent, or an acrylic resin-based polymer dispersing agent.

In the colorant 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 still more preferably 1 to 15 parts by weight, based on 100 parts by weight of the colorant. When the content of the dispersant is within the above range, uniform dispersion of the colorant in the colorant dispersion liquid according to the present invention becomes easier. In addition, since the smaller the upper limit is, the balance of each component tends to be better in the photosensitive resin composition described later, and the compounding amount of other components in the photosensitive resin composition can be relatively increased, so other characteristics such as sensitivity are improved. it becomes easier to do Regarding the sensitivity characteristic, the effect at the time of using the blue-type pigment which absorbs the photosensitive wavelength especially becomes favorable.

[oxime compound]

The colorant dispersion liquid according to the present invention contains an oxime compound represented by the following formula (1). This oxime compound has both a function as a photoinitiator and a function as a dispersing aid. Therefore, when the colorant dispersion containing the colorant contains the oxime compound, the dispersion stability of the colorant tends to be improved even if the content of the dispersant is reduced. That is, by using the oxime compound, it becomes easy to reduce the content of the dispersant in the colorant dispersion without impairing the dispersion stability of the colorant. As a result, a part of the dispersant is substituted with the oxime compound. Since the said oxime compound functions also as a photoinitiator, said substitution corresponds to reducing content of a dispersing agent and increasing content of a photoinitiator. Therefore, in the photosensitive resin composition obtained from the colorant dispersion containing the oxime compound, the content of the photopolymerization initiator can be increased, and it is easy to form a highly adherent micropattern with a low exposure amount from this photosensitive resin composition. The said oxime compound can be used individually or in combination of 2 or more types.

[Tue 7]

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

It is thought that an interaction occurs between the oxime compound and the colorant, and the oxime compound can improve the dispersion stability of the colorant. In particular, when the colorant is a pigment composed of a nitrogen-containing aromatic ring compound, it is considered as follows. In a pigment composed of a nitrogen-containing aromatic ring compound, the π electron system is in an unstable state due to the influence of the nitrogen atom contained in the molecule compared to the case where the nitrogen atom is not included. Therefore, it is difficult for the pigment which consists of a nitrogen-containing aromatic ring compound to have good dispersion stability. The oxime compound used in the pigment dispersion according to the present invention contains an oxime group and a carbonyl group, and since an aromatic ring is bonded to these groups, a stable π electron system is formed. It is presumed that a π-π interaction occurs between the pigment composed of the oxime compound and the nitrogen-containing aromatic ring compound, and the molecules of each other stack, thereby stabilizing the π electronic system of the pigment. As a result, it is thought that the said oxime compound can improve the dispersion stability of the pigment which consists of a nitrogen-containing aromatic ring compound.

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

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

When R ¹ is an organic group, R ¹ is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Preferred examples when R ¹ is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, Benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, 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 substituent a heterocyclylcarbonyl group that may be used, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

As for the number of carbon atoms of an alkyl group, when R ^<1> is an alkyl group, 1-20 are preferable and 1-6 are more preferable. Moreover, when R ^<1> is an alkyl group, it may be straight-chain or branched-chain. Specific examples when R ¹ is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group A real group, an isodecyl group, etc. are mentioned. Moreover, when R ^<1> is an alkyl group, the alkyl group may contain the ether bond (-O-) in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

As for the number of carbon atoms of an alkoxy group, when R ^<1> is an alkoxy group, 1-20 are preferable and 1-6 are more preferable. Moreover, when R ^<1> is an alkoxy group, it may be straight chain or branched chain. Specific examples in case R ¹ is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, etc. are mentioned. Moreover, when R ^<1> is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxy group. A propyloxy group etc. are mentioned.

As for the carbon atom number of a cycloalkyl group or a cycloalkoxy group, when R ^<1> is a cycloalkyl group or a cycloalkoxy group, 3-10 are preferable and 3-6 are more preferable. A cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group etc. are mentioned as a specific example in case R ^<1> is a cycloalkyl group. Specific examples in case R ¹ is a cycloalkoxy group include cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, and cyclooctyloxy group.

As for the carbon atom number of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, when R ^<1> is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, 2-21 are preferable and 2-7 are more preferable. Specific examples of when R ¹ is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexanoyl group, n -Heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentanoyl group A decanoyl group, and an n-hexadecanoyl group, etc. are mentioned. Specific examples in case R ¹ is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, and 2,2-dimethylpropanoyloxy group. , n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n- Tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

As for the carbon atom number of an alkoxycarbonyl group, when R ^<1> is an alkoxycarbonyl group, 2-20 are preferable and 2-7 are more preferable. Specific examples in case R ¹ is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxy group. carbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec- Octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group, etc. are mentioned.

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

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

When R ¹ is a heterocyclylcarbonyl group, the heterocyclyl groups included in the heterocyclylcarbonyl group are the same as those in the case where R ¹ is a heterocyclyl group.

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

Examples of the substituent in case the phenyl group, naphthyl group, and heterocyclyl group included in R ¹ further have a substituent include an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, and a carbon atom group of 2 to 7 carbon atoms. A saturated aliphatic acyl group, 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, an alkyl group having 1 to 6 carbon atoms Dialkylamino group, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, and cyano group having When the phenyl group, naphthyl group, and heterocyclyl group included in R ¹ further have substituents, the number of substituents is not limited to the range not impairing the object of the present invention, but is preferably 1 to 4. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ¹ have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, a nitro group or a group represented by R ⁶ -CO- as R ¹ is preferable because the sensitivity tends to improve. R ⁶ is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Examples of groups suitable for 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. Among these groups as R ⁶ , a 2-methylphenyl group, a thiophen-2-yl group, and an α-naphthyl group are particularly preferred.

In addition, when R ¹ is a hydrogen atom, transparency tends to be improved and is preferable. Transparency tends to be better when R ¹ is a hydrogen atom and R ⁴ is (R4-2 described later).

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

When R ² and R ³ are chain alkyl groups, the chain alkyl group may be either a straight chain alkyl group or a branched chain alkyl group. When R ² and R ³ are chain alkyl groups, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, and more preferably 1 to 6. Moreover, when R ^<1> is an alkyl group, it may be straight-chain or branched-chain. Specific examples when R ¹ is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group A real group, an isodecyl group, etc. are mentioned. Moreover, when R ^<1> is an alkyl group, the alkyl group may contain the ether bond (-O-) in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

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

When R ² and R ³ are aromatic cyclic hydrocarbon groups, the aromatic cyclic hydrocarbon group is preferably a phenyl group, a group formed by bonding of a plurality of benzene rings via a carbon-carbon bond, or a group formed by condensation of a plurality of benzene rings. When the aromatic cyclic hydrocarbon group is a phenyl group or a group formed by bonding or condensation of a plurality of benzene rings, the number of rings of benzene rings contained in the aromatic cyclic hydrocarbon group is not particularly limited, preferably 3 or less, more preferably 2 or less, and 1 This is particularly preferred. Preferred specific examples of the aromatic cyclic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

When R ² and R ³ are an aliphatic cyclic hydrocarbon group, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20 and more preferably 3 to 10. Examples of the monocyclic cyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, A tetracyclododecyl group, an adamantyl group, etc. are mentioned.

When R ² and R ³ are heteroaryl groups, the heteroaryl group is a 5-membered or 6-membered monocyclic ring containing one or more of N, S, and O, or a heteroaryl group formed by condensation of such monocycles or a benzene ring. When the heteroaryl group is a condensed ring, the number of rings is up to 3. Examples of the heterocycle constituting the heteroaryl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, Pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine , cinoline, and quinoxaline; and the like.

R ² and R ³ may combine with each other to form a spiro ring. It is preferable that the group which consists of a spiro ring formed by ^R2 and ^R3 is a cycloalkylidene group. When R ² and R ³ combine to form a cycloalkylidene group, the spiro ring constituting the cycloalkylidene group is preferably a 5-membered to 6-membered ring, more preferably a 5-membered ring.

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

Examples of preferred organic groups for R ⁴ include, as in R ¹ , an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, or a substituent; A phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, 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 heterocycle which may have a substituent A lyl group, a heterocyclylcarbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group. Specific examples of these groups are the same as those described for R ¹ . Moreover, as R ^<4> , a cycloalkylalkyl group, the phenoxyalkyl group which may have a substituent on the aromatic ring, and the phenylthioalkyl group which may have a substituent on the aromatic ring are preferable. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in R ¹ may have.

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

As mentioned above, although R ^<4> was demonstrated, as R ^<4> , the group represented by the following formula (R4-1) or (R4-2) is preferable.

[Tue 8]

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

Examples of organic groups for R ⁶ and R ⁷ in formula (R4-1) are the same as for R ¹ . As R ⁶ , an alkyl group or a phenyl group is preferable. As for the number of carbon atoms, when R ^<6> is an alkyl group, 1-10 are preferable, 1-5 are more preferable, 1-3 are especially preferable, and 1 is the most preferable. That is, R ⁶ is most preferably a methyl group. When R ⁶ and R ⁷ combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferable examples of the group represented by formula (R4-1) in which R ⁶ and R ⁷ form a ring include a naphthalen-1-yl group, a 1,2,3,4-tetrahydronaphthalen-5-yl group, and the like. can be heard In the formula (R4-1), p is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In the formula (R4-2), R ⁸ is an alkyl group. 1-10 are preferable, as for the number of carbon atoms of an alkyl group, 1-5 are more preferable, and 1-3 are especially preferable. As R ^<8> , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. are illustrated preferably, and among these, a methyl group is more preferable.

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

In formula (1), R ⁵ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As a substituent which may have when R ^<5> is an alkyl group, a phenyl group, a naphthyl group, etc. are illustrated preferably. Moreover, as a substituent which may have when R ^<1> is an aryl group, a C1-C5 alkyl group, an alkoxy group, a halogen atom, etc. are illustrated preferably.

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

When m is 0, the compound represented by Formula (1) can be synthesized, for example, according to Scheme 1 below. In Scheme 1, a fluorene derivative represented by the following formula (1-1) is used as a raw material. When R ¹ is a nitro group or a monovalent organic group, the fluorene derivative represented by formula (1-1) is a fluorene derivative in which the 9th position is substituted with R ² and R ³ by introducing substituent R ¹ by a known method. can get it A fluorene derivative in which the 9-position is substituted with R ² and R ³ , for example, when R ² and R ³ are alkyl groups, as described in Japanese Patent Laid-Open No. 06-234668, in the presence of an alkali metal hydroxide, It can be obtained by reacting fluorene with an alkylating agent in a protic polar organic solvent. In addition, an alkylating agent such as an alkyl halide, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide are added to an organic solvent solution of fluorene to carry out an alkylation reaction. , 9,9-alkyl substituted fluorenes can be obtained.

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

Next, the fluorene derivative represented by the obtained formula (1-3) is oxime-treated with hydroxylamine to obtain an oxime compound represented by the following formula (1-4). An oxime compound of formula (1-4), an acid anhydride ((R ⁵ CO) ₂ O) represented by formula (1-5) below, or an acid halide represented by formula (1-6) below (R ⁵ COHal, Hal is a halogen atom) to react to obtain a compound represented by the following formula (1-7).

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

<Scheme 1>

[Tue 9]

When m is 1, the compound represented by Formula (1) can be synthesize|combined according to the following scheme 2, for example. In Scheme 2, a fluorene derivative represented by the following formula (2-1) is used as a raw material. The fluorene derivative represented by Formula (2-1) is obtained by acylating the compound represented by Formula (1-1) by a Friedel Crafts reaction in the same manner as in Scheme 1. The fluorene derivative represented by formula (2-1) is reacted with a nitrite ester (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following general formula (2-2) in the presence of hydrochloric acid to obtain the following formula (2-3) A ketoxime compound represented by is obtained. Next, a ketoxime compound represented by the following formula (2-3) and an acid anhydride ((R ⁵ CO) ₂ O) represented by the following formula (2-4) or the following general formula (2-5) A compound represented by the following formula (2-6) can be obtained by reacting an acid halide (R ⁵ COHal, Hal is a halogen atom). Further, in the following formulas (2-1), (2-3), (2-4), (2-5), and (2-6), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ is the same as in formula (1).

When m is 1, there exists a tendency that the generation|occurrence|production of a foreign material in the pattern formed using the photosensitive composition containing the compound represented by Formula (1) can be reduced more.

<Scheme 2>

[Tue 10]

The following compounds are mentioned as a preferable specific example of the compound represented by Formula (1).

[Tue 11]

In the colorant dispersion according to the present invention, the content of the oxime compound is not particularly limited as long as the object of the present invention is not impaired. The content of the oxime compound is preferably 1 to 50 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the coloring agent. By making content of the said oxime compound into this range, the dispersion stability of a colorant tends to become favorable in the colorant dispersion liquid obtained. In addition, a colorant dispersion in which the content of the oxime compound is within the above range can be suitably used for preparing a photosensitive resin composition capable of forming highly adherent micropatterns with a low exposure amount.

Further, in the colorant dispersion according to the present invention, the total content of the dispersant and the oxime compound is preferably 1 to 60 parts by weight, more preferably 1 to 55 parts by weight, and 1 to 20 parts by weight based on 100 parts by weight of the colorant. Denial is more preferable. When the total content is in the above range, each component in the colorant dispersion liquid and the photosensitive resin composition obtained from the colorant dispersion liquid while ensuring uniform dispersion of the colorant in the colorant dispersion liquid according to the present invention and the effect of the oxime compound. The balance of is likely to be good. Moreover, since the compounding quantity of the other component in the said photosensitive resin composition can be relatively increased, so that an upper limit is small, it becomes easy to improve other characteristics, such as a sensitivity.

[solvent]

Examples of the solvent in the colorant dispersion according to the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol mono 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- (poly)alkylene glycol monoalkyl ethers such as n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; (Poly)alkylenes 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; lactate alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-Hydroxy-2-methylethylpropionate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, ethoxyethylacetate, hydroxyethylacetate, 2 -Hydroxy-3-methyl methyl butocarbonate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetic acid Butyl, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, acetoacetic acid other esters such as methyl, ethyl acetoacetate, and ethyl 2-oxobutanoate; Aromatic hydrocarbons, such as toluene and xylene; and amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. A solvent can be used individually or in combination of 2 or more types.

Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3- Methoxybutyl acetate is preferable because it can improve the dispersibility of the colorant while exhibiting excellent solubility for an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator described later, and a compound represented by the formula (1), It is particularly preferable to use propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate.

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

[Dispersion aids other than oxime compounds]

The colorant dispersion liquid according to the present invention may contain a dispersing aid other than the above oxime compound as an optional component. Dispersion aids other than the above oxime compounds are preferably dispersion aids having a nitrogen-containing aromatic ring in view of stacking properties. Since there is, it is preferable that it is a silane coupling agent which has a nitrogen-containing aromatic ring. As a silane coupling agent which has a nitrogen-containing aromatic ring, what is specifically represented by following formula (11) is preferable.

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

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

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

A silanol group formed by hydrolysis of an alkoxy group, R ¹¹ , reacts with the surface of the substrate and the like, thereby improving adhesion of a pattern formed using the photosensitive resin composition described later to the surface of the substrate. For this reason, it is preferable that p is 3 from the viewpoint of easily improving the adhesion of the pattern to the substrate surface.

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

In Formula (11), R ¹³ is an alkylene group. Regarding R ¹³ , the number of carbon atoms in the alkylene group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 2 to 4. Preferred specific examples of R ¹³ include a methylene group, a 1,2-ethylene group, a 1,1-ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a propane-1,1-diyl group, Propane-2,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-1,2-diyl group, butane-1,1-diyl group, butane-2,2 -diyl group, butane-2,3-diyl group, pentane-1,5-diyl group, pentane-1,4-diyl group, and hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, and dodecane-1,12-diyl group. there is. Among 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 -NH-, -O-, or -S-, preferably -NH-. Since the bond represented by -CO-NH- is less likely to undergo hydrolysis than the bond represented by -CO-O- or -CO-S-, a silane coupling agent in which Y is -NH- in the photosensitive resin composition described later When using, it is easy to form a pattern with excellent water resistance.

R ¹⁴ is a single bond or an alkylene group, preferably a single bond. Preferred examples in the case where R ¹⁴ is an alkylene group are the same as those for R ¹³ .

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

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

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

Preferred examples of X include groups of the following formula.

[Tue 12]

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

[Tue 13]

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

[Tue 14]

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

[Method for preparing colorant dispersion]

In the colorant dispersion according to the present invention, the colorant, the dispersant, the oxime compound, and the solvent are mixed (dispersed/kneaded) with an agitator such as a 3-roll mill, a ball mill, or a sand mill, and, if necessary, a 5 μm membrane filter or the like It can be prepared by filtering through a filter. It is thought that by mixing (dispersing/kneading) the coloring agent and the oxime compound (as a dispersing aid) together with a stirrer in preparation of a colorant dispersion, an interaction occurs between the colorant and the oxime compound to obtain the effect of the present invention. . In particular, when the colorant is a pigment made of a nitrogen-containing aromatic ring compound, the pigment made of a nitrogen-containing aromatic ring compound and the oxime compound (as a dispersing aid) are mixed (dispersed/kneaded) together with a stirrer as a preparation of a colorant dispersion liquid By this, it is thought that the effect of this invention is acquired because the π-π interaction arises between the pigment which consists of a nitrogen-containing aromatic ring compound, and the said oxime compound.

<Photosensitive resin composition>

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

[base resin]

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

As base resin, polymerizable resins, such as polymerizable group containing resin, are mentioned, for example. Examples of such polymerizable resins include those having an ethylenically unsaturated group among alkali-soluble resins described later.

Moreover, alkali-soluble resin is mentioned as base material resin. Alkali-soluble resin is a resin film having a film thickness of 1 µm formed on a substrate by a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by weight, and immersed in a KOH aqueous solution having a concentration of 0.05% by weight for 1 minute. It refers to dissolving with a film thickness of 0.01 µm or more at the time of application.

The alkali-soluble resin is not particularly limited as long as it is a resin exhibiting alkali-solubility as described above, and conventionally known alkali-soluble resins can be used. Alkali-soluble resin can be used individually or in combination of 2 or more types.

As an example of a preferable alkali-soluble resin, resin which has a cardo structure (A1) is mentioned. (A1) The resin having a cardo structure is not particularly limited, and conventionally known resins can be used. Especially, resin represented by the following formula (a-1) is preferable.

[Tuesday 15]

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

[Tue 16]

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

[Tue 17]

In the above formula (a-1), Y ^a represents a residue obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-endo-methylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, Anhydrous glutaric acid etc. are mentioned.

Moreover, in said formula (a-1), Z ^<a> represents the residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride.

Moreover, in said formula (a-1), m represents the integer of 0-20.

(A1) It is preferable that it is 1000-40000, and, as for the mass average molecular weight of resin which has a cardo structure, it is more preferable that it is 2000-30000. By setting it as said range, sufficient heat resistance and film strength can be obtained, obtaining favorable developability.

Moreover, as another example of a preferable alkali-soluble resin, (A2) epoxy resin is mentioned. (A2) It does not specifically limit as an epoxy resin, A conventionally well-known epoxy resin can be used, The thing which does not have an ethylenically unsaturated group or the thing which has an ethylenically unsaturated group may be sufficient.

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

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

In addition, in this specification, "(meth)acrylic acid" means both acrylic acid and methacrylic acid.

It is preferable that it is 5 to 29 weight%, and, as for the ratio of the structural unit (structural unit which has a carboxyl group) derived from the unsaturated carboxylic acid which occupies in the said resin (A2-1), it is more preferable that it is 10 to 25 weight%. By setting it as the said range, the developability of the photosensitive resin composition can be made suitable.

The epoxy group-containing unsaturated compound may not have an alicyclic epoxy group or may have an alicyclic epoxy group, but it is more preferable to 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)acrylate, and 6,7-epoxyheptyl. (meth)acrylic acid epoxyalkyl esters such as (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate; α-alkyl acrylic acid epoxyalkyl esters such as α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, and α-ethyl 6,7-epoxyheptyl acrylate; glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether; etc. can be mentioned. Among these, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, o - Vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferred.

The alicyclic group of the epoxy group-containing unsaturated compound having an alicyclic epoxy group may be monocyclic or polycyclic. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a monocyclic alicyclic group. Moreover, as a polycyclic alicyclic group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group, etc. are mentioned.

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

[Tue 18]

[Tue 19]

[Tue 20]

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

These epoxy group-containing unsaturated compounds can be used individually or in combination of 2 or more types.

The ratio of the structural unit (constitutive unit having an epoxy group) derived from an epoxy group-containing unsaturated compound in the resin (A2-1) is preferably 5 to 90% by weight, more preferably 15 to 75% by weight. By setting it as the said range, it becomes easy to form a color filter etc. of a favorable shape.

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

The alicyclic group of the alicyclic group-containing unsaturated compound may be monocyclic or polycyclic. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a monocyclic alicyclic group. Moreover, as a polycyclic alicyclic group, an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group, etc. are mentioned.

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

[Tue 21]

[Tue 22]

In the above formula, R ^a6 represents a hydrogen atom or a methyl group, R ^a7 represents a single bond or a divalent saturated 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, linear or branched alkylene group such as a methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, or hexamethylene group is preferable. As R ^a8 , a methyl group and an ethyl group are preferable, for example.

It is preferable that it is 1 to 40 weight%, and, as for the ratio of the structural unit derived from the alicyclic group containing unsaturated compound which occupies in the said resin (A2-1), it is more preferable that it is 5 to 30 weight%.

In addition, the resin (A2-1) may be further copolymerized with other compounds other than those described above. Examples of such other compounds include (meth)acrylic acid esters, (meth)acrylamides, aryl compounds, vinyl ethers, vinyl esters, and styrenes. These compounds can be used individually or in combination of 2 or more types.

Examples of (meth)acrylic acid esters include linear or branched chains such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, and t-octyl (meth)acrylate. Of alkyl (meth) acrylate; Chloroethyl (meth)acrylate, 2,2-dimethylhydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate, furfuryl (meth)acrylate; etc. can be mentioned.

As (meth)acrylamides, (meth)acrylamide, N-alkyl (meth)acrylamide, N-aryl (meth)acrylamide, N,N-dialkyl (meth)acrylamide, N,N-aryl (meth)acrylamide ) Acrylamide, N-methyl-N-phenyl (meth)acrylamide, N-hydroxyethyl-N-methyl (meth)acrylamide, etc. are mentioned.

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; etc. can be mentioned.

As vinyl ethers, 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-dimethylpropyl vinyl 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, etc. Alkyl vinyl ether of; 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; etc. can be mentioned.

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

Examples of styrene include styrene; Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene Alkyl styrene, such as acetoxymethyl styrene; Alkoxy styrene, such as methoxy styrene, 4-methoxy-3-methyl styrene, and dimethoxy styrene; Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl Halo styrene, such as styrene and 4-fluoro-3-trifluoromethyl styrene; etc. can be mentioned.

It is preferable that it is 2000-50000, and, as for the mass average molecular weight of Resin (A2-1), it is more preferable that it is 5000-30000. By setting it as the said range, there exists a tendency to balance the film-forming ability and developability of the photosensitive resin composition easily.

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

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

It is preferable that the ratio of the structural unit (constitutive unit having a carboxyl group) derived from an unsaturated carboxylic acid in the resins (A2-2) and (A2-3) is 5 to 60% by weight, more preferably 10 to 40% by weight. do. By setting it as the said range, the developability of the photosensitive resin composition can be made suitable.

Further, the ratio of the constituent units derived from the epoxy group-containing unsaturated compound (constitutive units having an epoxy group) in the resins (A2-2) and (A2-3) is preferably 5 to 90% by weight, and preferably 15 to 75% by weight. is more preferable. By setting it as the said range, it becomes easy to form a color filter etc. of a favorable shape.

It is preferable that it is 2000-50000, and, as for the mass average molecular weight of resin (A2-2) and (A2-3), it is more preferable that it is 5000-30000. By setting it as the said range, there exists a tendency to balance the film-forming ability and developability of the photosensitive resin composition easily.

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

It is preferable that it is 40 to 85 weight% with respect to solid content of the photosensitive resin composition, and, as for content of base resin, it is more preferable that it is 45 to 75 weight%. By setting it as said range, there exists a tendency for easy balance of developability.

[Photoinitiator]

The photopolymerization initiator is not particularly limited, and conventionally known photopolymerization initiators can be used. A photoinitiator can be used individually or in combination of 2 or more types.

Specifically as the photopolymerization initiator, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2 -Hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropyl phenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)- 2-hydroxy-2-methylpropan-1-one, bis(4-dimethylaminophenyl)ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid butyl, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl -β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, o-benzoylmethylbenzoate, 2,4-diethylthioxanthone , 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, Benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidal, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-diphenylimidazole 2 monomer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triaryl Imidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (i.e. Michler's ketone), 4,4'-bisdiethylaminobenzophenone (i.e. ethyl Michler's ketone) ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n -Butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone , 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl) Heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl ) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6- Bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-( 4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4, 6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl) -4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis -Trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl- s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-( 2-Bromo-4-methoxy)styrylphenyl-s-triazine, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1 -(O-acetyloxime), 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], 2-benzyl-2-dimethylamino-1-(4- Morpholinophenyl)-butanone-1,2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane -1-one, "NCI-831" (brand name: made by ADEKA), etc. are mentioned. Moreover, the oxime compound used by this invention can also be used as a photoinitiator. That is, in the photosensitive resin composition according to the present invention, the oxime compound is contained as a dispersion aid (included as a dispersion aid in the colorant dispersion), but may also be contained as a photopolymerization initiator. In this case, it is thought that interaction does not arise between the oxime compound as a photoinitiator and a coloring agent. In particular, when the colorant is a pigment composed of a nitrogen-containing aromatic ring compound, it is considered that π-π interaction does not occur between the oxime compound as a photopolymerization initiator and the pigment composed of a nitrogen-containing aromatic ring compound. About the oxime compound as a photoinitiator, it is the same as the above, and the compound represented by said Formula (1) is preferable.

It is preferable that content of a photoinitiator is 0.5 to 20 weight% with respect to solid content of the photosensitive resin composition. By setting it as the said range, sufficient heat resistance and chemical-resistance can be obtained, and also the ability to form a coating film can be improved and curing failure can be suppressed.

In addition, when the photosensitive resin composition contains the oxime compound as a photopolymerization initiator, the ratio of the oxime compound is preferably 1 to 100% by weight, more preferably 20 to 100% by weight, based on the total amount of the photopolymerization initiator. , It is more preferably 50 to 100% by weight, and particularly preferably 80 to 100% by weight. By setting it as the said range, the sensitivity of the photosensitive resin composition and thin wire adhesiveness can be improved.

[colorant dispersion]

The content of the colorant dispersion according to the present invention may be appropriately determined depending on the use of the photosensitive resin composition. As an example, the content of the colorant in the photosensitive resin composition is preferably 5 to 70% by weight with respect to the solid content of the photosensitive resin composition. And, the amount to be 25 to 60% by weight is more preferable.

In the case of using the photopolymerizable monomer described later, the content of the colorant dispersion according to the present invention is 0.01 to 2.5 parts by weight based on 100 parts by weight of the total amount of the base resin and the photopolymerizable monomer. The amount to be added is preferable, and the amount to be 0.01 to 0.5 parts by weight is more preferable. By adjusting the content of the colorant dispersion according to the present invention so that the content of the oxime compound in the photosensitive resin composition falls within this range, it is easy to form a fine pattern having excellent adhesion to a substrate.

[Photopolymerizable monomer]

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

Monofunctional monomers include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, and butoxymethoxymethyl. (meth)acrylamide, N-methylol(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citracone acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate , 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate Late, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth) Acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) ) acrylates, half (meth)acrylates of phthalic acid derivatives, and the like. These monofunctional monomers can be used alone or in combination of two or more.

On the other hand, as the multifunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate ) Acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di ( meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri( meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxy Diethoxyphenyl) propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol di Glycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether Poly(meth)acrylate, urethane(meth)acrylate (i.e., tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl(meth)acrylate, methylenebis(meth) polyfunctional monomers such as acrylamide, (meth)acrylamide methylene ether, and condensates of polyhydric alcohols and N-methylol (meth)acrylamide; triacryl formal; and the like. These polyfunctional monomers can be used individually or in combination of 2 or more types.

It is preferable that it is 1 to 30 weight% with respect to the solid content of the photosensitive resin composition, and, as for content of a photopolymerizable monomer, it is more preferable that it is 5 to 20 weight%. By setting it as the said range, there exists a tendency to balance sensitivity, developability, and resolution easily.

[Other Ingredients]

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

<Method for producing photosensitive resin composition>

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

In the method for producing a photosensitive resin composition according to the present invention, a colorant dispersion is prepared by mixing a colorant, a dispersant, the oxime compound, and a solvent in advance, and the colorant dispersion is mixed with other components such as a base resin. By passing through such a process, the photosensitive resin composition which can form a highly adhesive micropattern even with a low exposure amount is obtained.

[ Example ]

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

In the following Examples and Comparative Examples, the following Compounds 1 to 3 and Comparative Compounds 1 and 2 were used as oxime compounds.

[Tue 23]

<Synthesis of oxime compound>

Hereinafter, synthesis examples 1-4 demonstrate the synthesis of compounds 1-3.

[Synthesis Example 1]

(Synthesis of 9,9-di-n-propylfluorene)

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

[Synthesis Example 2]

(Synthesis of 2-nitro-9,9-di-n-propylnitrofluorene)

After adding 9.18 g (40 mmol) of copper diacetate trihydrate to a mixed solvent composed of 131 ml of acetic acid and 262 ml of acetic anhydride, the mixed solvent was stirred for 10 minutes. Thereafter, a solution in which 10.02 g (40 mmol) of 9,9-di-n-propylfluorene obtained by the method of Synthesis Example 1 was dissolved in 131 ml of acetic acid was slowly added in multiple portions to the mixed solvent. Next, a nitration reaction was performed by stirring a mixed solvent containing 9,9-di-n-propylfluorene for 3 hours. After the reaction, the reaction mixture was poured into a beaker containing ice water. After collecting the precipitate by filtration, the precipitate was washed and dried to obtain 10.76 g of 2-nitro-9,9-di-n-propylfluorene (yield: 91%).

[Synthesis Example 3]

(Synthesis of Compound 1)

4.10 g (16.37 mmol) of 9,9-di-n-propylfluorene and 3.04 g (18.00 mmol) of (2-methylphenyl)acetic acid chloride were cooled on ice in a dichloromethane solvent, 50 ml, in the presence of 2.62 g of aluminum chloride ( It was reacted for 1 hour under cold and cold. The reaction mixture was opened in ice water, and the organic layer was separated. The recovered organic layer was dried over anhydrous magnesium sulfate and then evaporated. The residue was purified on a silica gel column with ethyl acetate/hexane = 1/2 as the eluent to obtain 5.95 g (15.55 mmol) of 2-(2-methylphenyl)acetyl-9,9-di-n-propylcarbazole. 5.95 g (15.55 mmol) of 2-(2-methylphenyl)acetyl-9,9-di-n-propylcarbazole and 1.60 g (15.55 mmol) of concentrated hydrochloric acid were mixed with 2.42 g (23.33 mmol) of isobutyl nitrite in the presence of dimethyl In 25 ml of formamide solvent, it was made to react under ice-cooling for 3 hours. The reaction solution was evaporated, ethyl acetate was added to the residue, washed with saturated brine, dried over anhydrous magnesium sulfate, and then evaporated to obtain 2-[2-methylphenyl(hydroxyimino)acetyl]-9,9-di-n-propyl 4.80 g (11.67 mmol) of carbazole was obtained. 4.80 g (11.67 mmol) of 2-[2-methylphenyl(hydroxyimino)acetyl]-9,9-di-n-propylcarbazole and 1.43 g (13.42 mmol) of acetic anhydride and 1.36 g (13.42 mmol) of triethylamine and 45.00 ml of a dimethylformamide solvent were mixed and stirred at 35°C for 3 hours. After cooling to room temperature, ethyl acetate was added to the reaction solution, washed with water, dried over anhydrous magnesium sulfate, and then evaporated. The residue was purified on a silica gel column with ethyl acetate/hexane = 2/1 as the eluent to obtain 4.76 g (10.50 mmol, yield 72%) of compound 1. The measurement results of ¹ H-NMR of Compound 1 were as follows.

¹ H-NMR (600 MHz, CDCl ₃ , ppm): 8.25 (d, 1H), 8.22 (s, 1H), 7.83 (d, 1H), 7.81 (dd, 1H), 7.33-7.40 (m, 3H), 7.26-7.33 (m, 4H), 2.35 (s, 3H), 2.14 (s, 3H), 1.95-2.07 (m, 4H), 0.63-0.66 (m, 10H).

[Synthesis Example 4]

(Synthesis of Compound 2)

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

After dissolving 8.56 g (20 mmol) of the obtained pale yellow solid and 1.5 g (21 mmol) of hydroxylamine hydrochloride in 100 ml of ethanol, the ethanol solution was refluxed for 2 hours. After ethanol was distilled off from the reaction liquid after refluxing, the residue was washed off. After the washed residue was dissolved in ethyl acetate, the ethyl acetate solution was dried over magnesium sulfate. From the ethyl acetate solution after drying, ethyl acetate was removed using a rotary evaporator to obtain an oxime compound (2-methylphenyl(7-nitro-9,9-di-n-propylfluorene 2-yl)ketone oxime) as a residue. After dissolving the obtained oxime body in 60 ml of THF, acetyl chloride (3.45 g, 44 mmol) was added in THF and reaction was carried out while stirring. After the reaction, triethylamine (4.7 g, 46 mmol) was added dropwise to the reaction solution at room temperature. Precipitation of the salt was confirmed with dripping. After stirring the reaction solution to which triethylamine was added for 2 hours, 40 ml of water was added to the reaction solution. Then, the product in the reaction solution was extracted with 40 ml of ethyl acetate. The organic layer was washed twice with 40 ml of water, and then washed twice with 40 ml of a saturated aqueous solution of potassium carbonate. After drying the washed organic layer with magnesium sulfate, the solvent was removed from the organic layer using a rotary evaporator to obtain a residue. The residue was purified by silica gel column chromatography (developing solvent, ethyl acetate:n-hexane = 1:1 (weight ratio)) to obtain 6.63 g (16.81 mmol, yield 84%) of compound 2. The measurement results of ¹ H-NMR of Compound 2 were as follows.

¹ H-NMR (600 MHz, CDCl ₃ , ppm): 8.2 (d, 1H), 8.23 (s, 1H), 7.79-7.83 (m, 4H), 2.48 (s, 3H), 2.27 (s, 3H), 2.06-2.12 (m, 4H), 0.51-0.68 (m, 10H).

[Synthesis Example 5]

(Synthesis of Compound 3)

(2-methylphenyl) acetic acid chloride 3.04g (18.00mmol) was replaced with 3-cyclopentylpropionic acid chloride 2.89g (18.00mmol) in the same manner as in Synthesis Example 3, Compound 3, 4.46g (10.02mmol, yield 72%) ) was obtained. The measurement results of ¹ H-NMR of Compound 3 were as follows.

¹ H-NMR (600 MHz, CDCl ₃ , ppm): 8.06-8.12 (m, 2H), 7.71-7.78 (m, 2H), 7.31-7.40 (m, 3H), 2.52 (d, 2H), 2.27 (s) , 3H), 1.89-2.19 (m, 5H), 1.48-1.80 (m, 6H), 1.19-1.26 (m, 2H), 0.61-0.77 (m, 10H).

<Preparation of colorant dispersion>

[Examples 1 to 30, Comparative Examples 1 to 8]

The colorant shown in Table 1, the dispersant, and the oxime compound were mixed and dissolved in the solvent shown in Table 1 to prepare a colorant dispersion liquid having a solid content concentration of 17 to 23% by weight. In addition, the amount of use of each component is as shown in Table 1. In addition, the detail of a coloring agent, a dispersing agent, and a solvent is as follows. Mixture 1 of Example 10 is a mixture (weight ratio 1:1) of Compound 1 (oxime compound) synthesized above and a silane coupling agent having a nitrogen-containing aromatic ring represented by the following formula. In addition, mixture 2 of Example 20 is a mixture of compound 2 (oxime compound) synthesized above and a silane coupling agent having a nitrogen-containing aromatic ring represented by the following formula (weight ratio 1:1). In addition, mixture 3 of Example 30 is a mixture of compound 3 (oxime compound) synthesized above and a silane coupling agent having a nitrogen-containing aromatic ring represented by the following formula (weight ratio: 1:1).

[Tue 24]

·coloring agent

R254 (C.I. Pigment Red 254, a diketopyrroropyrrole pigment represented by the formula on the far left below)

B15:6 (C.I. Pigment Blue 15:6, a phthalocyanine-based pigment represented by the formula in the middle below)

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

Perylene (3,4,9,10-perylenetetracarboxydiamide: in the above formula (e-3), ^Re7 and ^Re8 are hydrogen atoms)

[Tue 25]

・Dispersing agent

Acrylic resin polymer dispersant (trade name: Disper BYK 2001, manufactured by Big Chemie)

·solvent

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

[Evaluation of viscosity]

The viscosity of the colorant dispersion immediately after preparation was measured using an E-type clay meter (manufactured by Tokyo Keiki). In addition, the colorant dispersion liquid was filled in a light-shielding glass container and allowed to stand at 40°C for 7 days in an airtight state, and then the viscosity of the colorant dispersion liquid was measured again using an E-type clay meter. When the difference between the viscosity value immediately after preparation and the viscosity value after standing at 40 ° C. for 7 days is 0.3 mPa s or less, the dispersion stability of the colorant dispersion is judged to be good (○), and the difference exceeds 0.3 mPa s In this case, the dispersion stability of the colorant dispersion was judged to be poor (×). The results are shown in Table 1.

As shown in Table 1, in Examples 1, 2, 4 to 10, 11, 12, 14 to 20, 21, 22, and 24 to 30, by adding compounds 1, 2 or 3, even if the content of the dispersant is reduced, the colorant The dispersion stability of was good. On the other hand, in Comparative Examples 1 to 8 in which all of Compounds 1 to 3 were not used, Examples 1, 2, 4 to 10, 11, 12, 14 to 20, 21, 22, and 24 to 30 used a larger amount of dispersant than In this case, the dispersion stability of the colorant becomes good, or even if a larger amount of the dispersant is used than in Examples 1, 2, 4 to 10, 11, 12, 14 to 20, 21, 22, and 24 to 30, the colorant is dispersed. Stability was poor. From the above, it can be seen that the colorant dispersion according to the present invention has good dispersion stability of the colorant even when the content of the dispersant is reduced.

<Preparation of photosensitive resin composition>

[Examples 31 to 66 and Comparative Examples 9 to 19]

20 parts by weight of the photopolymerization initiator described in Table 2 or 3, 30 parts by weight of resin A (solid content 55% by weight, solvent: 3-methoxybutyl acetate), 30 parts by weight of dipentaerythritol hexaacrylate, and Table 2 or 3 100 parts by weight, 3-methoxybutyl acetate (60% by weight) and propylene glycol monomethyl After mixing a mixed solvent composed of ether acetate (40% by weight), it was filtered through a membrane filter having a pore diameter of 5 µm to prepare a photosensitive resin composition. Moreover, the quantity of the mixed solvent was adjusted and the solid content concentration in the photosensitive resin composition was adjusted to 15 weight%.

Moreover, among the photoinitiators shown in Table 2 or 3, details of "OXE01", "Compound 1+OXE01", and "Compound 2+OXE01" are as follows.

OXE01: BASF 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)

Compound 2+OXE01: A mixture of Compound 2 and OXE01 (weight ratio 1:1)

Moreover, what was synthesize|combined according to the following prescription was used for resin A used as preparation of the photosensitive resin composition.

First, in a 500 ml four-necked flask, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid were added. and dissolved by heating at 90 to 100°C while blowing air into it at a rate of 25 mL/min. Next, while the solution was in a cloudy state, the temperature was gradually raised and heated to 120°C to completely dissolve the solution. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. In the meantime, heat stirring was continued until the acid value was measured and it became less than 1.0 mgKOH/g. Twelve hours were required until the acid value reached the target value. And it cooled to room temperature, and the bisphenol fluorene type|mold epoxy acrylate represented by the following structural formula (a-4) of a colorless and transparent solid state was obtained.

[Tue 26]

Next, 600 g of 3-methoxybutyl acetate was added to and dissolved in 307.0 g of the bisphenol fluorene type epoxy acrylate obtained in this way, and then 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, The temperature was gradually raised and reacted at 110 to 115°C for 4 hours. After confirming disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, and it was made to react at 90 degreeC for 6 hours, and resin A was obtained. Disappearance of the acid anhydride group was confirmed by IR spectrum. This resin A corresponds to the compound represented by the above general formula (a-1).

About each of the photosensitive resin compositions of Examples 31-66 and Comparative Examples 9-19, evaluation of the coloring by post-baking and evaluation of thin wire adhesiveness were performed according to the following method. Results are shown in Tables 2 and 3.

[Evaluation of coloring]

About each of the photosensitive resin compositions of Examples 31-66 and Comparative Examples 9-19, coloring evaluation was performed in the following procedure.

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

[Evaluation of fine wire adhesion]

The photosensitive resin compositions of Examples 31 to 66 and Comparative Examples 9 to 19 were applied on a glass substrate (100 mm × 100 mm) using a spin coater, and prebaked at 90 ° C. for 120 seconds to form a coating film having a thickness of 1.0 μm. . Next, using a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the coating film was irradiated with ultraviolet rays through a negative mask having an exposure gap of 50 µm and a line pattern of 5 µm. The exposure amount was 20, 50, 100, and 200 mJ/cm ² in four stages. A line pattern was formed by performing post-bake at 230 degreeC for 30 minutes after image development for 40 second for the coating film after exposure with 0.04 weight% KOH aqueous solution at 26 degreeC.

The formed line pattern was observed with an optical microscope to evaluate thin wire adhesion. Thin wire adhesion was evaluated as "good" when a line pattern was formed without peeling off from the substrate, and "poor" when the line pattern was not peeled off from the substrate. Results are shown in Tables 2 and 3.

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

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

Further, in Comparative Examples 10 to 13, 18, and 19, a line pattern of 5 μm adheres to the substrate at an exposure amount of 50 mJ/cm ² , and especially in Comparative Examples 10, 18, and 19, a low exposure amount of 20 mJ/cm ² is sufficient. , a line pattern of 5 μm adhered to the substrate. However, in Comparative Examples 10 to 13, 18, and 19, coloring due to heating at the time of post-baking could not be suppressed. Although the photosensitive resin compositions of Comparative Examples 11 and 13 contain Compound 1 as a photopolymerization initiator, it is considered that no interaction has occurred between Compound 1 and the colorant because coloring cannot be suppressed, and more specifically, the colorant Considering that it is a pigment composed of a nitrogen-containing aromatic ring compound, it is considered that a π-π interaction did not occur between Compound 1 and the pigment composed of a nitrogen-containing aromatic ring compound.

Further, in Comparative Example 16, coloration due to heating during post-baking could not be suppressed, and at an exposure amount of 50 mJ/cm ² , the 5 μm line pattern did not adhere to the substrate, and the thin wire adhesion was higher than in Examples 31 to 66. was falling behind

Claims (6)

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

(R ¹ is a hydrogen atom, a nitro group, or a group represented by R ⁶ -CO-, and R ⁶ is 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, or a substituent It is a heterocyclyl group which may have, R ² and R ³ are each a chain alkyl group, a cyclic hydrocarbon group, or a heteroaryl group, R ² and R ³ may combine with each other to form a spiro ring, and R ⁴ is represented by the following formula ( R4-2), R ⁵ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and m is 0 or 1.)

(In formula (R4-2), q is an integer of 1 to 8, r is an integer of 1 to 5, s is an integer of 0 to (r+3), and R ⁸ is an alkyl group.) The method of claim 1,
A colorant dispersion in which m is 1. The method of claim 1,
The colorant dispersion liquid in which R ¹ is a hydrogen atom. A photosensitive resin composition comprising a base resin, a photopolymerization initiator, and the colorant dispersion of any one of claims 1 to 3. Dispersion aid which consists of an oxime compound represented by following formula (1).
[Tue 3]

(R ¹ is a hydrogen atom, a nitro group, or a group represented by R ⁶ -CO-, and R ⁶ is 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, or a substituent It is a heterocyclyl group which may have, R ² and R ³ are each a chain alkyl group, a cyclic hydrocarbon group, or a heteroaryl group, R ² and R ³ may combine with each other to form a spiro ring, and R ⁴ is represented by the following formula ( R4-2), R ⁵ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and m is 0 or 1.)

(In formula (R4-2), q is an integer of 1 to 8, r is an integer of 1 to 5, s is an integer of 0 to (r+3), and R ⁸ is an alkyl group.) delete