JP6210691B2 - Pigment dispersion and method for producing photosensitive resin composition using the same - Google Patents

Description

  The present invention relates to a pigment dispersion and a method for producing a photosensitive resin composition using the same, and particularly suitable for a photosensitive resin composition for forming a black matrix and / or a color filter used in a display such as a liquid crystal panel. The present invention relates to a pigment dispersion and a method for producing a photosensitive resin composition using the same.

  The liquid crystal panel includes a black matrix for enhancing the contrast of an image, and a color filter in which an RGB colored layer generally composed of red (R), green (G), and blue (B) colors is formed. . In these black matrixes and color filters, a photosensitive resin composition in which black or each color pigment is dispersed is applied to a substrate and dried, and then the obtained coating film is exposed and developed to form a desired pattern. It is formed by repeating.

  In recent years, from the viewpoint of further improving productivity, such a photosensitive resin composition is required to be able to form a pattern having a good shape even with a low exposure amount. Moreover, in order to ensure the reliability of a product, the said photosensitive resin composition is calculated | required to have high adhesiveness which closely_contact | adheres to a board | substrate, even when a micro pattern is formed.

  In order to produce the photosensitive resin composition, a pigment dispersion in which a pigment is dispersed is used. For example, Patent Document 1 discloses a pigment dispersion containing a pigment, a dispersion medium, and a specific organic compound having a carboxyl group or the like. The pigment dispersion is required to have good dispersibility of the pigment even after aging.

JP 2004-46047 A

The present invention has been made in view of such a conventional situation. For example, the dispersibility of the pigment is good after several days , and a fine pattern with high adhesion can be formed with a low exposure amount. It is an object of the present invention to provide a pigment dispersion capable of giving a photosensitive resin composition even after aging and a method for producing a photosensitive resin composition using the same.

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

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

（式中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子又は有機基を示す。ただし、Ｒ^１及びＲ^２の少なくとも一方は有機基を示す。Ｒ^１及びＲ^２は、それらが結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。Ｒ^３は、単結合又は有機基を示す。Ｒ^４及びＲ^５は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、又は有機基を示す。Ｒ^６、Ｒ^７、Ｒ^８、及びＲ^９は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基を示す。ただし、Ｒ^６及びＲ^７が水酸基となることはない。Ｒ^６、Ｒ^７、Ｒ^８、及びＲ^９は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。Ｒ^１０は、水素原子又は有機基を示す。）

(Wherein, ^{R 1} and ^{R 2} each independently represent a hydrogen atom or an organic group. However, .R ¹ and ^{R 2} represents an organic group at least one of the ^{R 1} and ^{R 2} are they are attached It may form a cyclic structure and may contain a heteroatom bond, R ³ represents a single bond or an organic group, and R ⁴ and R ⁵ each independently represents a hydrogen atom, a halogen atom, or a hydroxyl group , mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group .R ^6, R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group Shows a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group, or an organic group. However, never R ⁶ and R ⁷ is a hydroxyl group .R ^6, R ⁷ , R ⁸ , and R ⁹ may be bonded to each other to form a cyclic structure, and may include a heteroatom bond, and R ¹⁰ may be a hydrogen atom or an organic group. Show.)

  The 2nd aspect of this invention is a manufacturing method of the photosensitive resin composition including the process of mixing an alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, and the said pigment dispersion.

  According to the present invention, a pigment dispersion capable of providing a photosensitive resin composition having good dispersibility of a pigment after aging and capable of forming a fine pattern with a low exposure amount and high adhesion even after aging, and the pigment dispersion The manufacturing method of the photosensitive resin composition using this can be provided.

It is a graph which shows the particle size distribution of the pigment dispersion liquid left to stand at 40 degreeC in the presence or absence of the compound represented by the said Formula (1) for 4 days.

<Pigment dispersion>
The pigment dispersion according to the present invention contains at least a pigment, a solvent, and a compound represented by the above formula (1). The pigment dispersion according to the present invention does not contain a photopolymerizable compound such as a photopolymerizable monomer or a photopolymerization initiator.

[Pigment]
The pigment dispersion according to the present invention contains a pigment. The pigment dispersion according to the present invention is preferably used, for example, as a color filter forming application for a liquid crystal display by containing a pigment. Further, the pigment dispersion according to the present invention is preferably used, for example, as a black matrix forming application in a color filter by containing a light shielding agent as a pigment. The pigments can be used alone or in combination of two or more.

  Although it does not specifically limit as a pigment, For example, the compound classified into the pigment (Pigment) in the color index (CI; issue of The Society of Dyers and Colorists), for example, the following color It is preferable to use an index (CI) number.

C. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same, and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180 185;
C. I. Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46 49, 51, 55, 59, 61, 63, 64, 71, 73;
C. I. Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same, and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;
C. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same, and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49 : 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64 : 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155 166, 168, 170, 171, 172, 174, 175, 176, 177, 78, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;
C. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same, and only the number is described) 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 66;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37;
C. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigment brown 28;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

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

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

  Resin-coated carbon black has lower electrical conductivity than carbon black without resin coating, so when used as a black matrix for liquid crystal display, it produces less current leakage and produces a highly reliable display with low power consumption. it can.

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

  In addition, the inorganic pigment and the organic pigment may be used alone or in combination, but when used in combination, the organic pigment is added in an amount of 10 to 10 parts by mass with respect to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. It is preferably used in the range of 80 parts by mass, and more preferably in the range of 20 to 40 parts by mass.

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

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

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

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

[Compound represented by Formula (1)]
The pigment dispersion according to the present invention contains a compound represented by the following formula (1). When the pigment dispersion contains a compound represented by the following formula (1), the dispersibility of the pigment tends to be good even after aging. Moreover, even when the pigment dispersion containing the compound represented by the following formula (1) is used for the preparation of the photosensitive resin composition after the lapse of time, the resulting photosensitive resin composition has a low exposure amount. A highly adhesive micropattern can be formed. The compounds represented by the following formula (1) can be used alone or in combination of two or more.

In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom or an organic group, but at least one of R ¹ and R ² represents an organic group.
Examples of the organic group in R ¹ and R ² include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. This organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.
This organic group is usually monovalent, but can be a divalent or higher organic group when a cyclic structure is formed.

R ¹ and R ² may be bonded to each other to form a cyclic structure, and may further include a hetero atom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a condensed ring.

The bond other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as the effect of the present invention is not impaired, and includes a bond containing a hetero atom such as an oxygen atom, a nitrogen atom, or a silicon atom. It is done. Specific examples include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (—N═C (—R) —, —C (═NR) —: R is A hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and the like.
From the viewpoint of heat resistance, the bond other than the hydrocarbon group in the organic group of R ¹ and R ² includes an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond ( -N = C (-R)-, -C (= NR)-: R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, or a sulfinyl bond.

The substituent other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as the effect of the present invention is not impaired, and is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group. , Cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy Group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxyimino group, alkyl ether group, alkenyl ether group, alkyl thioether group, alkenyl thioether group, aryl ether group, aryl thioether Group, an amino group _{(-NH 2, -NHR, -NRR '} : R and R' each independently represent a hydrocarbon group). The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.
Substituents other than hydrocarbon groups in the organic groups of R ¹ and R ² include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyano groups, cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanato groups, silyl groups. Group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, A phosphinyl group, a phosphono group, a phosphonato group, a hydroxyimino group, an alkyl ether group, an alkenyl ether group, an alkyl thioether group, an alkenyl thioether group, an aryl ether group, and an aryl thioether group are preferred.

Among the above, as R ¹ and R ² , at least one of them is an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms, or a heterocycloalkyl group having 2 to 20 carbon atoms bonded to each other. Alternatively, it preferably forms a heteroaryl group. Examples of the heterocycloalkyl group include a piperidino group and a morpholino group, and examples of the heteroaryl group include an imidazolyl group and a pyrazolyl group.

In the above formula (1), R ³ represents a single bond or an organic group.
Examples of the organic group for R ³ include groups in which one hydrogen atom has been removed from an alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, aryl group, aralkyl group, and the like. This organic group may contain a substituent in the organic group. Examples of the substituent include those exemplified for R ¹ and R ² . Further, this organic group may be either linear or branched.

Among these, R ³ is preferably a single bond, or a group in which one hydrogen atom is removed from an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms.

In the above formula (1), R ⁴ and R ⁵ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group. A group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group;
Examples of the organic group for R ⁴ and R ⁵ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

Among these, R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, or 7 carbon atoms. -16 aryloxyalkyl group, C7-20 aralkyl group, C2-C11 alkyl group having a cyano group, C1-C10 alkyl group having a hydroxyl group, C1-C10 alkoxy group , An amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms (-COOR, -OCOR: R represents a hydrocarbon group. ), An aryl group having 6 to 20 carbon atoms, an electron donating group and / or an electron withdrawing group substituted with an aryl group having 6 to 20 carbon atoms, an electron donating group and / or an electron withdrawing group substituted benzyl group , Amino group is preferably a methylthio group. More preferably, both R ⁴ and R ⁵ are hydrogen atoms, or R ⁴ is a methyl group and R ⁵ is a hydrogen atom.

In the above formula (1), R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, A sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group, or an organic group is shown.
Examples of the organic group for R ⁶ , R ⁷ , R ⁸ , and R ⁹ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

In the above formula (1), R ⁶ and R ⁷ do not become a hydroxyl group. When R ⁶ or R ⁷ is a hydroxyl group, as described in Patent Document 2, a cyclization reaction occurs due to electromagnetic wave irradiation and heating. For this reason, even if such a compound is contained in the photosensitive resin composition, light energy is consumed for cyclization, and good micropatterning characteristics cannot be obtained. On the other hand, the compound represented by the above formula (1) does not cause a cyclization reaction because R ⁶ and R ⁷ do not become a hydroxyl group, and is favorable when contained in the photosensitive resin composition. Micropatterning characteristics can be obtained.

Two or more of R ⁶ , R ⁷ , R ⁸ , and R ⁹ may be bonded to form a cyclic structure, and may include a hetero atom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a condensed ring. For ^{example, R 6, R 7, R} 8, and ^{R 9} may combine two or more of ^{them, R 6, R 7, R} 8, and share an atom of the benzene ring ^{to which R 9} is attached A condensed ring such as naphthalene, anthracene, phenanthrene, and indene may be formed.

Among these, R ⁶ , R ⁷ , R ⁸ , and R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, or a group having 4 to 13 carbon atoms. A cycloalkenyl group, an aryloxyalkyl group having 7 to 16 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, carbon C1-C10 alkoxy group, C2-C11 amide group, C1-C10 alkylthio group, C1-C10 acyl group, C2-C11 ester group, C6-C20 Aryl group, electron donating group and / or electron withdrawing group substituted aryl group having 6 to 20 carbon atoms, electron donating group and / or electron withdrawing group substituted benzyl group, cyano group, methylthio group, nitro On the basis Preferably there is.
In addition, as R ⁶ , R ⁷ , R ⁸ , and R ⁹ , two or more of them are bonded to share a benzene ring atom to which R ⁶ , R ⁷ , R ⁸ , and R ⁹ are bonded. In the case where condensed rings such as naphthalene, anthracene, phenanthrene, and indene are formed, it is preferable from the viewpoint that the absorption wavelength becomes longer.
More preferably, all of R ⁶ , R ⁷ , R ⁸ , and R ⁹ are hydrogen atoms, or any one of R ⁶ , R ⁷ , R ⁸ , and R ⁹ is a nitro group, and the remaining 3 One is a hydrogen atom.

In the formula ^{(1), R 10} represents a hydrogen atom or an organic group.
Examples of the organic group for R ¹⁰ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.
Since the compound represented by the above formula (1) has an —OR ¹⁰ group at the para-position of the benzene ring, the solubility in an organic solvent is good.

Among these, R ¹⁰ is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group.

  Among the compounds represented by the above formula (1), particularly preferred specific examples include compounds represented by the following formulas.

  The method for synthesizing the compound represented by the above formula (1) is not particularly limited, but it can be synthesized according to the method described in Examples described later.

  In the pigment dispersion according to the present invention, the content of the compound represented by the formula (1) is not particularly limited as long as the object of the present invention is not impaired. The content of the compound represented by the formula (1) is typically preferably 0.1 to 30 parts by mass, and 0.5 to 20 parts by mass with respect to 100 parts by mass of the pigment. It is more preferable. By setting the content of the compound represented by the above formula (1) in such a range, the resulting pigment dispersion is likely to have good pigment dispersibility even after aging. Moreover, the pigment dispersion liquid in which the content of the compound represented by the formula (1) is in the above range prepares a photosensitive resin composition capable of forming a fine pattern with high adhesion at a low exposure amount. It can be used suitably.

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

  Examples of the dispersant include known ones, and it is preferable to use a polyethyleneimine polymer dispersant, a urethane resin polymer dispersant, and an acrylic resin polymer dispersant. In particular, when carbon black is used as the pigment, it is preferable to use an acrylic resin polymer dispersant as the dispersant.

  In the pigment dispersion according to the present invention, the content of the dispersant is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the pigment. . When the content of the dispersant is in the above range, uniform dispersion of the pigment in the pigment dispersion according to the present invention is further facilitated.

[Method for preparing pigment dispersion]
In the pigment dispersion according to the present invention, a pigment, a solvent, a compound represented by the following formula (1), and a dispersant as necessary are mixed (dispersed and kneaded) with a stirrer such as a three-roll mill, a ball mill, or a sand mill. And it can prepare by filtering with filters, such as a 5 micrometer membrane filter, as needed.

<Photosensitive resin composition>
The photosensitive resin composition obtained by the method for producing a photosensitive resin composition according to the present invention contains at least an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a pigment dispersion according to the present invention. To do.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Photopolymerizable monomer]
It does not specifically limit as a photopolymerizable monomer, A conventionally well-known monofunctional monomer and a polyfunctional monomer can be used. A photopolymerizable monomer can be used individually or in combination of 2 or more types.

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

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

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

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

  Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, bis (4-dimethylaminophenyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4- Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- ( o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobu Tyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- ( o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4 ' -Bisdimethylaminobenzophenone (ie Michler's ketone), 4 4′-bisdiethylaminobenzophenone (ie, ethyl Michler's ketone), 4,4′-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p -Dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroaceto Enone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9 -Acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s- Triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s- Triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl)- -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, IRGACURE OXE02 ”,“ IRGACURE OXE01 ”,“ IRGACURE 369 ”,“ IRGACURE 651 ”,“ IRGACURE 907 ”(trade name: manufactured by BASF),“ NCI-831 ”(trade name: manufactured by ADEKA), and the like.

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

[Pigment dispersion]
The content of the pigment dispersion according to the present invention may be appropriately determined according to the use of the photosensitive resin composition. As an example, the content of the pigment in the photosensitive resin composition is a solid content of the photosensitive resin composition. The amount of 5 to 70% by mass is preferable with respect to the minute, and the amount of 25 to 60% by mass is more preferable.
In particular, when forming the black matrix using the photosensitive resin composition, the amount of the pigment dispersion in the photosensitive resin composition is adjusted so that the OD value per 1 μm of the film thickness of the black matrix is 4 or more. It is preferable to adjust. If the OD value per 1 μm of film thickness in the black matrix is 4 or more, a sufficient display contrast can be obtained when used in the black matrix of a liquid crystal display.

  Furthermore, the content of the pigment dispersion according to the present invention is such that the content of the compound represented by the above formula (1) in the photosensitive resin composition is 100 mass in total of the alkali-soluble resin and the photopolymerizable monomer. The amount of 0.01 to 2.5 parts by mass is preferable with respect to parts, and the amount of 0.01 to 0.5 parts by mass is more preferable. By adjusting the content of the pigment dispersion according to the present invention so that the content of the compound represented by the above formula (1) in the photosensitive resin composition falls within this range, the adhesiveness to the substrate is excellent. It becomes easy to form a minute pattern.

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

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

  In the method for producing a photosensitive resin composition according to the present invention, a pigment dispersion is prepared by previously mixing a pigment and the compound represented by the above formula (1), and this pigment dispersion is mixed with another alkali-soluble resin or the like. Mix with ingredients. By passing through such a process, even if it is a case where the pigment dispersion liquid after time-lapse is used, the photosensitive resin composition which can form a highly adhesive micropattern with a low exposure amount is obtained.

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

<Compound represented by the above formula (1)>
As the compound represented by the above formula (1), compounds 1 to 12 represented by the following formula were prepared. The synthesis method of these compounds 1-12 is shown below.

[Synthesis Method of Compound 1]
3- (4-Methoxyphenyl) acrylic acid chloride 5.90 g (30 mmol) was dissolved in 50 ml of dry ether, triethylamine 4.59 ml (equivalent ratio 1.1), diethylamine 2.41 ml (equivalent ratio 1.1). And stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 1 (4.65 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis Method of Compound 2]
6.32 g (30 mmol) of 2-methyl-3- (4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, 2.41 ml (equivalent ratio) of diethylamine. 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 2 (4.93 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis Method of Compound 3]
7.25 g (30 mmol) of 3- (2-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, 2.41 ml (equivalent ratio) of diethylamine. 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 3 (5.55 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis Method of Compound 4]
7.25 g (30 mmol) of 3- (3-nitro-4-methoxyphenyl) acrylic chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, 2.41 ml (equivalent ratio) of diethylamine. 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 4 (5.55 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis Method of Compound 5]
7.67 g (30 mmol) of 2-methyl-3- (2-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, 4.59 ml of triethylamine (equivalent ratio 1.1), diethylamine 2. 41 ml (equivalent ratio 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 5 (5.83 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis Method of Compound 6]
2.67 g (30 mmol) of 2-methyl-3- (3-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, 4.59 ml of triethylamine (equivalent ratio 1.1), diethylamine 2. 41 ml (equivalent ratio 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 6 (5.83 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis Method of Compound 7]
3- (4-Methoxyphenyl) acrylic acid chloride 5.90 g (30 mmol) was dissolved in 50 ml of dry ether, and triethylamine 4.59 ml (equivalent ratio 1.1) and imidazole 2.25 ml (equivalent ratio 1.1). And stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 7 (3.41 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis Method of Compound 8]
6.32 g (30 mmol) of 2-methyl-3- (4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, 2.25 ml (equivalent ratio) of imidazole. 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 8 (3.62 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis Method of Compound 9]
7.25 g (30 mmol) of 3- (2-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, 2.25 ml (equivalent ratio) of imidazole. 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 9 (4.08 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis Method of Compound 10]
7.25 g (30 mmol) of 3- (3-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, 2.25 ml (equivalent ratio) of imidazole. 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 10 (4.08 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis Method of Compound 11]
7.67 g (30 mmol) of 2-methyl-3- (2-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, imidazole 2. 25 ml (equivalent ratio 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 11 (4.29 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis Method of Compound 12]
7.67 g (30 mmol) of 2-methyl-3- (3-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml (equivalent ratio 1.1) of triethylamine, imidazole 2. 25 ml (equivalent ratio 1.1) was added and stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 12 (3.41 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

<Preparation of pigment dispersion>
[Example 1]
The following pigment and the compound represented by the above formula (1) are mixed, and 3-methoxybutyl acetate (MA) / propylene glycol monomethyl ether acetate (PM) / cyclohexanone (AN) = 60/20/20 (mass ratio). A pigment dispersion having a solid content concentration of 15% by mass was prepared.
Pigment Carbon dispersion “CF black” (trade name: manufactured by Mikuni Dye Co., Ltd., solid content 25%, solvent: 3-methoxybutyl acetate): 1200 parts by mass Compound represented by the above formula (1) Compound 1 ..50 parts by mass

[Comparative Example 1]
A pigment dispersion was prepared in the same manner as in Example 1 except that Compound 1 was not used.

[Evaluation]
The pigment dispersions of Example 1 and Comparative Example 1 were allowed to stand at 40 ° C. for 4 days. For the pigment dispersion after standing, the zeta potential was measured using ESA9800 (manufactured by Matec Applied Sciences), and the particle size distribution and average particle size were measured using LB-550 (manufactured by Horiba Seisakusho). The results are shown in Table 1 and FIG.

  As shown in Table 1, the zeta potential is the pigment dispersion of Example 1 containing the compound represented by the above formula (1) and the pigment dispersion of Comparative Example 1 not containing the compound represented by the above formula (1). Did not show any significant difference. On the other hand, as shown in Table 1, the average particle diameter of the pigment dispersion liquid of Example 1 was smaller than that of Comparative Example 1. Regarding the particle size distribution, the pigment dispersion of Example 1 formed a single peak distribution, whereas the pigment dispersion of Comparative Example 1 formed a bimodal distribution. From the above, the pigment dispersion containing the compound represented by the above formula (1) has better dispersibility of the pigment after the lapse of time compared with the pigment dispersion containing no compound represented by the above formula (1). It turns out that it is.

<Preparation of photosensitive resin composition>
[Example 2]
The following pigment and the compound represented by the above formula (1) are mixed, and 3-methoxybutyl acetate (MA) / propylene glycol monomethyl ether acetate (PM) / cyclohexanone (AN) = 60/20/20 (mass ratio). A pigment dispersion having a solid content concentration of 15% by mass was prepared. This pigment dispersion was allowed to stand at 40 ° C. for 3 days. The pigment dispersion after standing, the alkali-soluble resin, the photopolymerizable monomer, and the photopolymerization initiator are mixed, and 3-methoxybutyl acetate (MA) / propylene glycol monomethyl ether acetate (PM) / cyclohexanone (AN) = 60. / 20/20 (mass ratio) was dissolved in a mixed solvent to prepare a photosensitive resin composition having a solid content concentration of 15% by mass.
-Alkali-soluble resin Resin (A-1) (solid content 55%, solvent: 3-methoxybutyl acetate) ... 310 parts by mass-Photopolymerizable monomer dipentaerythritol hexaacrylate (DPHA) ... 65 parts by mass Photopolymerization initiator "OXE-02" (trade name: manufactured by BASF) ... 15 parts by mass-Compound represented by the above formula (1) Compound 1 ... 5 parts by mass-Pigment Carbon dispersion "CF "Black" (trade name: Mikuni Color Co., Ltd., solid content 25% solvent: 3-methoxybutyl acetate) ... 1200 parts by mass

The synthesis method of the resin (A-1) is as follows.
First, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid Was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target value. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by the following transparent formula (a-4) colorless and transparent.

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

[Examples 3 to 13]
A photosensitive resin composition was prepared in the same manner as in Example 2 except that the compounds 2 to 12 were used instead of the compound 1, respectively.

[Comparative Example 2]
A photosensitive resin composition was prepared in the same manner as in Example 2 except that Compound 1 was not used.

[Comparative Examples 3 to 14]
A pigment dispersion is prepared without using the compound represented by the above formula (1), the pigment dispersion after standing, the alkali-soluble resin, the photopolymerizable monomer, the photopolymerization initiator, and the above formula (1). A photosensitive resin composition was prepared in the same manner as in Examples 2 to 13 except that the compounds represented were mixed.

[Evaluation]
The photosensitive resin compositions of Examples 2 to 13 and Comparative Examples 2 to 14 were applied on a glass substrate (100 mm × 100 mm) using a spin coater, prebaked at 90 ° C. for 120 seconds, and a film thickness of 1.0 μm. The coating film was formed. Next, a mirror projection aligner (product name: TME-150 RTO, manufactured by Topcon Co., Ltd.) was used, the exposure gap was 50 μm, and the coating film was irradiated with ultraviolet rays through a negative mask on which a 5 μm line pattern was formed. The exposure amount was set in four stages of 10, 20, 40, and 100 mJ / cm ² . The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26 ° C. for 40 seconds and then post-baked at 230 ° C. for 30 minutes to form a line pattern.

  In addition, the photosensitive resin compositions of Examples 2 to 13 and Comparative Examples 2 to 14 were allowed to stand at 25 ° C. for 7 days, and the line patterns were formed in the same manner as described above using the photosensitive resin compositions after standing. Formed.

  The formed line pattern was observed with an optical microscope, and fine line adhesion was evaluated. The fine line adhesion was evaluated as “good” when the line pattern was formed without being peeled from the substrate, and “none” when the line pattern was not formed when peeled from the substrate. The results are shown in Table 2.

In the photosensitive resin compositions of Examples 2 to 13, the pigment dispersion containing compounds 1 to 12 represented by the above formula (1) was allowed to stand at 40 ° C. for 3 days, and the pigment dispersion after standing And other components such as an alkali-soluble resin. As can be seen from Table 2, when the photosensitive resin compositions of Examples 2 to 13 were used, a 5 μm line pattern adhered to the substrate even at a low exposure amount of 10 mJ / cm ² . The photosensitive resin compositions of Examples 2 to 13, which were allowed to stand at 25 ° C. for 7 days, showed similar fine wire adhesion.

On the other hand, in the photosensitive resin composition of Comparative Example 2, the pigment dispersion containing no compound represented by the above formula (1) was allowed to stand at 40 ° C. for 3 days, and the pigment dispersion after standing And other components such as an alkali-soluble resin. During the mixing after the standing, the compound represented by the formula (1) was not added. As can be seen from Table 2, when the photosensitive resin composition of Comparative Example 2 was used, the 5 μm line pattern was in close contact with the substrate only at an exposure amount of 20 mJ / cm ² or more. In addition, when the photosensitive resin composition of Comparative Example 2 that was allowed to stand at 25 ° C. for 7 days was used, the 5 μm line pattern was in close contact with the substrate only with an exposure amount of 100 mJ / cm ² or more.

Further, the photosensitive resin compositions of Comparative Examples 3 to 14 were prepared by allowing a pigment dispersion containing no compound represented by the above formula (1) to stand at 40 ° C. for 3 days. It is obtained by mixing with other components such as an alkali-soluble resin. During mixing after standing, the compound represented by the above formula (1) was added. As can be seen from Table 2, when the photosensitive resin compositions of Comparative Examples 3 to 14 were used, the 5 μm line pattern adhered to the substrate only at an exposure amount of 20 mJ / cm ² or more. Similar results were obtained when the photosensitive resin compositions of Comparative Examples 3 to 14 were allowed to stand at 25 ° C. for 7 days.

Claims (4)

A pigment dispersion containing a pigment, a solvent, and a compound represented by the following formula (1), and containing no photopolymerizable compound and photopolymerization initiator.

(Wherein, ^{R 1} and ^{R 2} each independently represent a hydrogen atom or an organic group. However, .R ¹ and ^{R 2} represents an organic group at least one of the ^{R 1} and ^{R 2} are they are attached It may form a cyclic structure and may contain a heteroatom bond, R ³ represents a single bond or an organic group, and R ⁴ and R ⁵ each independently represents a hydrogen atom, a halogen atom, or a hydroxyl group , mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group .R ^6, R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group Shows a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group, or an organic group. However, never R ⁶ and R ⁷ is a hydroxyl group .R ^6, R ⁷ , R ⁸ , and R ⁹ may be bonded to each other to form a cyclic structure, and may include a heteroatom bond, and R ¹⁰ may be a hydrogen atom or an organic group. Show.)   The pigment dispersion according to claim 1, further comprising a dispersant. A preparation step for preparing the pigment dispersion according to claim 1 or 2,
A mixing step of mixing the prepared pigment dispersion, alkali-soluble resin, photopolymerizable monomer, and photopolymerization initiator to obtain a photosensitive resin composition;
The manufacturing method of the photosensitive resin composition containing this.   Furthermore, the manufacturing method of Claim 3 including the stationary process which leaves the said pigment dispersion liquid between the said preparation process and the said mixing process.

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