JP4595374B2 - Black photosensitive resin composition - Google Patents

Description

  The present invention relates to a black photosensitive resin composition and a colored pattern formed using the same, and more particularly to a colored pattern constituting a color filter, particularly a black matrix.

The color filter (6) is, for example, an optical element that is incorporated into a liquid crystal display device and used to color a display image of the device, or is incorporated into a solid-state imaging device and used to obtain a color image. And what consists of a coloring pattern (5) formed adjacent to each other on the same plane on the substrate (2) is known. Here, the coloring pattern includes, for example, three primary color pixels of a red pixel (5R), a green pixel (5G), and a blue pixel (5B), and a black matrix (5BM) formed at the boundary of each color pixel. It is done. Here, each color pixel is a transparent layer colored in each color, and the black matrix is a layer that is black and does not substantially transmit visible light.
As a method for producing such a color filter (6), a colored photosensitive resin composition layer (1) comprising a solid content of the colored photosensitive resin composition is formed on a substrate (2) (FIG. 2 (a)), After irradiating the layer (1) with the light beam (4) through the photomask (3) (FIG. 2 (b)), the non-light-irradiated region (11) is dissolved in the developer to give a colored pattern (5). A method of forming is known (FIG. 2 (c)). The color filter (6) can be formed by repeating the above operation while changing the color of the pigment contained in the colored photosensitive resin composition and sequentially forming a colored pattern of each color (FIGS. 3 to 4). .

It has been conventionally known that certain O-acyloxime compounds act as photopolymerization initiators (see, for example, Patent Documents 1 and 2). Moreover, the method of applying an O-acyl oxime type compound to the light transmissive photosensitive resin composition was conventionally known (for example, refer patent documents 3-4 etc.).
However, in such a conventional method, the development margin of the colored photosensitive resin composition layer (1) is lowered and the width of appropriate development conditions becomes extremely narrow, or the resolution of the resulting colored pattern is lowered. There was a case. For this reason, in order to form a colored pattern stably, the development conditions must be managed very finely, and when a fine colored pattern is formed, the yield tends to decrease. Such a decrease in development margin and a decrease in resolution were particularly remarkable when forming a black matrix (5BM) that does not transmit light among the colored patterns (5).

  By the way, a method of applying a polycarboxylic acid resin obtained by modifying an epoxy compound to a black photosensitive resin composition has been conventionally known (see, for example, Patent Document 5). Here, in order to form a thinner black matrix, it is necessary to increase the concentration of the pigment contained in the colored photosensitive resin composition. However, if the concentration of the pigment is increased, the conventional method is sensitive to light. However, it was necessary to extend the irradiation time in order to secure the amount of light irradiation, and the decrease in productivity was remarkable.

JP, 2000-80068, page 7, right column, line 26-page 9, right column, line 48 JP-T 2002-538241 No. 22 page 15 line 22 page 17 line 17 JP-A-2001-264530, page 19, right column, line 15-page 21, right column, line 22 JP-A-2001-261661, page 8, left column, line 28-page 9, right column, line 8 JP, 2002-156753, A page 14 right column 22 line -16 page right column 40 line

  An object of the present invention is to provide a new black photosensitive resin composition capable of forming a colored pattern with a wide development margin, high resolution, and high sensitivity.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a certain type of photopolymerization initiator in combination with a specific resin.
That is, the present invention contains a black colorant (A), a binder resin (B), an addition-polymerizable compound (C) having an ethylenically unsaturated bond, and at least one photopolymerization initiator (D). A black photosensitive resin composition, wherein the binder resin (B) reacts an unsaturated monocarboxylic acid with a reaction product of a compound having two or more epoxy groups and a polybasic carboxylic acid, A polycarboxylic acid resin (b1) obtained by reacting an anhydride and a compound obtained by reacting an unsaturated monocarboxylic acid with a compound having two or more epoxy groups and further reacting with an anhydride of a polybasic carboxylic acid. A black photosensitive resin which is at least one polycarboxylic acid resin selected from the group consisting of carboxylic acid resins (b2), and wherein the photopolymerization initiator (D) contains an oxime compound. It provides compositions.

  The present invention also provides a color pattern formed using the black photosensitive resin composition, a color filter including the color pattern, and a display device including the color filter.

  According to the black photosensitive resin composition of the present invention, it is possible to form a colored pattern, particularly a black matrix, with good resolution, development margin and sensitivity, and to improve the yield of the color filter and thus the liquid crystal display device.

The black colorant (A) contained in the black photosensitive resin composition of the present invention is one or a mixture of two or more pigments, which may be inorganic pigments or organic pigments. Or a mixture thereof. Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and the like. Examples thereof include metal oxides and composite metal oxides. The organic pigment is specifically classified as a pigment in the Color Index (published by The Society of Dyers and Colorists). Compounds.
The black colorant (A) may be a mixture of one kind or two or more kinds of black pigments. By mixing a red pigment, a green pigment, a blue pigment, a yellow pigment, a cyan pigment, a magenta pigment, and the like. A colorant for obtaining black may be used.
Examples of the black pigment include carbon black, graphite described in JP-A-5-311109, JP-A-6-11613, and the like, JP-A-4-322219, JP-A-3-274503, and the like. Inorganic black pigments, azo black dyes described in JP-A-2-216102, and the like; I. Pigment black 1, C.I. I. Organic black pigments such as CI Pigment Black 7 can be used.
Examples of red pigments, green pigments, blue pigments, yellow pigments, cyan pigments, and magenta pigments that can be used in combination include C.I. I. Pigment Yellow 1 (hereinafter, CI Pigment Yellow is omitted and only the number is described. Other hues are also described in the same manner) 3, 12, 13, 14, 15, 16, 17, 20 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175;
C. I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;
C. I. Pigment violet 1, 19, 23, 29, 32, 36, 38;
C. I. Pigment Red 1, 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, 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, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 2 7,208,209,215,216,220,224,226,242,243,245,254,255,264,265;
C. I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Pigment green 7, 36;
C. I. And CI pigment brown 23 and 25.
Further, the black photosensitive resin composition using the black pigment may further contain, as a pigment, the red pigment, the green pigment, the blue pigment, the yellow pigment, the cyan pigment, the magenta pigment, and the like exemplified above. .
The black colorant used in the black photosensitive resin composition of the present invention can preferably contain at least one selected from the group consisting of carbon black and coated carbon black.

  The particle size of the pigment that can be used in the black photosensitive resin composition of the present invention is preferably 0.005 μm to 0.5 μm, more preferably 0.01 μm to 0.3 μm, in terms of average particle size. The pigment having the above particle diameter can be produced, for example, by a known method such as a kneader method, a sulfuric acid method, or an alkali reduction dissolution method.

  The surface of the pigment may be modified with a polymer or the like. Examples of the polymer include polymers described in JP-A-8-259876 and various commercially available pigment dispersion polymers. Specific examples include acrylic resins, vinyl chloride-vinyl acetate resins, maleic acid resins, ethyl cellulose resins, nitrocellulose resins, and the like. The form of the processed pigment treated with the resin is preferably a powder, paste, or pellet in which the resin and the pigment are uniformly dispersed.

  The content of the pigment in the black photosensitive resin composition is usually 20% or more and 70% or less, preferably 30% or more and 60% or less, based on the solid content after the volatile component is volatilized.

  The binder resin (B) used in the black photosensitive resin composition of the present invention is a component that gives the black photosensitive resin composition layer the property of dissolving the light-irradiated region in the developer. It functions as a dispersion medium for dispersing the pigment in the conductive resin composition layer and the formed colored pattern.

The binder resin (B) can be obtained by reacting an unsaturated monocarboxylic acid with a reaction product of a divalent or higher valent epoxy compound and a polybasic carboxylic acid, and further reacting with an anhydride of the polybasic carboxylic acid. From the group consisting of polycarboxylic acid resin (b2) obtained by reacting polycarboxylic acid resin (b1) and divalent or higher epoxy compound with unsaturated monocarboxylic acid and further reacting with anhydride of polybasic carboxylic acid At least one polycarboxylic acid resin selected is used.
As the divalent or higher epoxy compound, for example, at least one compound selected from the group consisting of formula (VIII) and formula (IX) is preferable.

[In Formula (VIII), p represents the average number of repeating units and represents an integer of 1 or more and 20 or less.
R ^{16 to} R ¹⁹ each independently represents a hydrogen atom, an alkyl having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. To express.
Q ^{1 to} Q ¹¹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an alkynyl group having 1 to 8 carbon atoms, or an alkyl group having 5 to 12 carbon atoms. Cycloalkyl, an aryl group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyloxy group having 1 to 8 carbon atoms, an alkynyloxy group having 1 to 8 carbon atoms, A C6-C14 aryloxy group, a nitro group, or a cyano group is represented. ],

[In Formula (IX), Q ^{12 to} Q ¹⁵ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms.
Y represents a single bond or a divalent residue represented by any one of formulas (IX-1) to (IX-8).
R ²⁰ represents an alkylene group having 1 to 10 carbon atoms.
q represents an integer of 0 to 5. ]

The polybasic carboxylic acid may be a saturated carboxylic acid or an unsaturated carboxylic acid. For example, maleic acid, succinic acid, itaconic acid, citraconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid , Methyl endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, 4,4'-diphthalic acid and other biphenyl tetracarboxylic acids, biphenyl ether tetracarboxylic acid Etc.
The polybasic carboxylic acid may be a corresponding acid anhydride such as maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, and the like.
The above polybasic acids or acid anhydrides thereof can be used alone or in admixture of two or more.
Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. The unsaturated monocarboxylic acids can be used alone or in admixture of two or more.
Examples of the polycarboxylic acid resin that can be used as the binder resin (B) include, for example, a polycondensation product of a compound represented by the formula (X) and a polybasic acid or an anhydride thereof (JP-A-4-355450, No. 9-40745, JP-A 09-325494, JP-A 2000-281738, etc.), an epoxy compound and a polybasic carboxylic acid and / or a monocarboxylic acid which is a precursor of the formula (X) A polycarboxylic acid resin obtained as a polycondensation product of a reaction product with a polybasic acid or an anhydride thereof, a reaction product obtained by reacting an epoxy compound represented by formula (XI) with a polyvalent carboxylic acid; A polycarboxylic acid resin obtained by reacting with an unsaturated group-containing monocarboxylic acid to obtain a new reactant and further reacting with an acid anhydride, an epoxy having the formula (XII) The reaction of the compound and a carboxylic acid, and the like polycarboxylic acid resin obtained by reacting a polybasic carboxylic acid or its anhydride.

[Wherein, R ²¹ and R ²² each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms.
R ²³ represents an alkylene group having 1 to 10 carbon atoms which may have a substituent.
R ²⁴ represents a hydrogen atom or a methyl group.
Y ¹ represents a divalent residue represented by any ^one of formulas (X-1) to (X-6).
q ¹ represents an integer of 0 to 5.
q ² is an integer from 1 to 10. ]

[Wherein, R ²⁵ and R ²⁶ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms.
Y ² represents a single bond or a divalent residue represented by any one of formulas (XI-1) to (XI-8).

R ²⁷ represents an alkylene group having 1 to 10 carbon atoms.
R ²⁸ represents a hydrogen atom, an alkyl group or a glycidyl group.
q ³ is an integer of 0-5.
q ⁴ is an integer of 0. However, if the q ⁴ is an integer of 2 to 10, repeating units in R ²⁵ to R ²⁸ which is different from, may be the same or different. ]

[Wherein, p ′ represents the average number of repeating units and takes a numerical value of 1 or more and 20 or less.
R ′ ^{16 to} R ′ ¹⁹ represent a methyl group.
P ′ ^{1 to} P ′ ⁴ and P ′ ^{9 to} P ′ ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 6 to 12 carbon atoms. ]
Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid Examples include acids, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid such as 4,4′-diphthalic acid, and biphenyl ether tetracarboxylic acid. Examples of the polybasic anhydride include acid anhydrides of the above polybasic acids. The above polybasic acids or acid anhydrides thereof can be used alone or in admixture of two or more.
Reactions between an epoxy compound and a carboxylic acid, and a reaction in which a reaction product of an epoxy compound and a carboxylic acid is further reacted with a polybasic carboxylic acid or an anhydride thereof include, for example, JP-A-9-80220 and JP-A-8-278630. For example, JP-A-8-278629, JP-A-7-64282, JP-A-7-64281, and JP-A-5-339356. The reaction is performed by mixing the compounds to be reacted. Reaction is normally performed at 20-250 degreeC, and you may use a solvent as needed. The obtained polycarboxylic acid resin may be used as it is in the reaction mixture, or may be used after a commonly performed extraction operation such as concentration, solvent distillation, reprecipitation, crystallization, and the like.

The amount of the polybasic acid or polybasic acid anhydride used is the total amount of the compound to be reacted such as the compounds represented by formulas (VIII) to (XII) and the polybasic acid or polybasic acid anhydride The molar ratio is preferably 5% or more and 95% or less, and more preferably 10% or more and 90% or less.
The acid value of the condensation polymer obtained by the above reaction is preferably 70 to 170, and more preferably 80 to 140.
The molecular weight of the above-mentioned polymer is usually 1,000 or more and 50,000 or less, more preferably 1,500 or more and 20,000 or less in terms of polystyrene-equivalent weight average molecular weight.

  The binder resin is generally 5% or more and 90% or less, preferably 10% or more and 60% or less, more preferably 20% or more and 45% or less, in mass fraction with respect to the solid content of the black photosensitive resin composition. It is used in the range.

As the compound (C) having an ethylenically unsaturated bond and capable of addition polymerization used in the black photosensitive resin composition of the present invention, for example, at least one ethylenically unsaturated bond at the end, preferably 2 or more It may be a monomer, a prepolymer such as a dimer, trimer or oligomer, a mixture thereof or a copolymer thereof.
Examples of the monomer include an ester of an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid and an aliphatic polyhydric alcohol compound, and an unsaturated carboxylic acid and an aliphatic polyhydric compound. And amides with a polyvalent amine compound.
Examples of the ester of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, and propylene glycol diester. Acrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene Glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetra Acrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, acrylic acid esters, such as sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer;
Tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, penta Erythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl Dimethyl meta , Methacrylic acid esters, such as bis [p- (methacryloxyethoxy) phenyl] dimethyl methane;
Ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetrataconate, etc. Itaconic acid ester;
Crotonic acid esters such as ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate;
Isocrotonic acid esters such as ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate;
Mention may be made of maleic esters such as ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate and sorbitol tetramaleate.
Examples of the amide of the unsaturated carboxylic acid and the aliphatic polyvalent amine compound include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, and 1,6-hexamethylene bis-methacrylamide. , Diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Other examples of the monomer include a vinylurethane compound obtained by adding a vinyl monomer represented by the formula (XIII) to a polyisocyanate compound having two or more isocyanate groups in one molecule.

[Wherein, R ²⁹ and R ³⁰ each independently represents a hydrogen atom or a methyl group. ]

  Examples of the vinyl urethane compound include compounds containing two or more polymerizable vinyl groups in one molecule (for example, Japanese Patent Publication No. 48-41708). Further, urethane acrylates such as those described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, etc. Polyfunctional acrylates and methacrylates such as polyester acrylates are also exemplified. Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  The use amount of the compound having an ethylenically unsaturated bond and capable of addition polymerization is usually 0.5% to 50%, preferably 1% to 40% by mass fraction with respect to the solid content of the composition. Hereinafter, it is more preferably 5% or more and 20% or less.

  The black photosensitive resin composition of this invention contains an oxime type compound as a photoinitiator (D). The oxime compound is preferably at least one photopolymerization initiator selected from the group consisting of formulas (I) to (IV).

[In formulas (I) to (IV), R ^{1 to} R ¹⁵ each have the following meaning.
R ¹ represents a phenyl group [the phenyl group is at least one selected from the group consisting of a halogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, —OR ⁸ , —SR ⁹ and —NR ¹⁰ R ¹¹ . It may be substituted by a group. ], A methyl group, an alkyl group having 2 to 20 carbon atoms [the alkyl group may be interrupted by one or more of -O-, and / or substituted by one or more of hydroxy groups. ], A cycloalkyl group having 5-8 carbon atoms, alkanoyl group having 2 to 20 carbon atoms, a benzoyl group [wherein the benzoyl group is an alkyl group, a phenyl group having 1 to 6 carbon atoms, -OR ^8, -SR ⁹ and - It may be substituted with at least one selected from the group consisting of NR ¹⁰ R ¹¹ . ], An alkoxycarbonyl group having 2 to 12 carbon atoms [the alkoxycarbonyl group may be interrupted by one or more of —O— and / or substituted by one or more of hydroxy groups. ], A phenoxycarbonyl group [the phenoxycarbonyl group is composed of at least one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, a phenyl group, —OR ⁸ , —SR ⁹ and —NR ¹⁰ R ^11. May be substituted. ], - CONR ¹⁰ R ¹¹ group, a cyano group, a nitro group, halogenated alkyl group [the halogen atom of from 1 to 4 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. ], - ^{SO-Z 1} [wherein, ^{Z 1} represents an alkyl group having 1 to 6 carbon atoms. ], - SO ₂ -Z ¹ [wherein, ^{Z 1} are as defined above. ^{], - Z 2 -SO-Z} 3 [ wherein, Z ² represents an alkylene group having 1 to 12 carbon atoms. Z ³ represents an aryl group having 6 to 12 carbon atoms. _{^{], - Z 4 -SO 2 -Z}} 3 [ wherein, ^{Z 4} represents an alkylene group having 1 to 12 carbon atoms. Z ³ represents the same meaning as described above. ], - in SO ₂ ^{O-Z 5} [wherein, ^{Z 5} represents an aryl group having 6 to 10 carbon atoms. Or a diphenyl-phosphinoyl group.

R ² represents an alkanoyl group having 2 to 12 carbon atoms [the alkanoyl group may be substituted with one or more halogen atoms or cyano groups. ], An alkenoyl group having 4 to 6 carbon atoms [wherein the double bond of the alkenoyl group is not conjugated with the carbonyl group. A benzoyl group [the benzoyl group is substituted by at least one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, —OR ⁸ , —SR ⁹ and —NR ¹⁰ R ^11. It may be. ], A C2-C6 alkoxycarbonyl group or a phenoxycarbonyl group [this phenoxycarbonyl group may be substituted by a C1-C6 alkyl group or a halogen atom. ].

R ^{3 to} R ⁷ are each independently a hydrogen atom, a halogen atom, a cyclopentyl group, a cyclohexyl group, or a phenyl group [the phenyl group is selected from the group consisting of —OR ⁸ , —SR ⁹ and —NR ¹⁰ R ^11. Optionally substituted with at least one group. ], A benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms [wherein the alkoxycarbonyl group is interrupted by one or more of -O-, and / or It may be substituted by one or more of the hydroxyl groups. ], Phenoxycarbonyl group, —OR ⁸ , —SR ⁹ , —SOR ⁹ , —SO ₂ R ⁹ or —NR ¹⁰ R ¹¹ [wherein —OR ⁸ , —SR ⁹ and —NR ¹⁰ R ¹¹ represent R ³ formation and one of the carbon atoms of the substituent or the phenyl ring of the phenyl rings present, a 5- or 6-membered ring via a single group formed by removing a hydrogen atom of R ⁸ to R ¹¹ as to R ⁷ May be. However, when forming a ring, R < ⁸ > -R < ¹¹ > is not a hydrogen atom. ]. However, at least one of R ^{3 to} R ⁷ is selected from the group consisting of —OR ⁸ , —SR ⁹ and —NR ¹⁰ R ¹¹ .

R ⁸ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms [the alkyl group is —OH, —SH, a cyano group, an alkoxy group having 1 to 4 carbon atoms, an alkeneoxy group having 3 to 6 carbon atoms, — _{OCH 2 CH 2 CN, -OCH 2} CH 2 (CO) O-T 1 ( where T ¹ represents an alkyl group having 1 to 4 carbon atoms.), - O (CO) -Z 6 ( wherein, Z ⁶ represents an alkyl group having 1 to 4 carbon atoms.), —O (CO) —Ph (wherein Ph represents a phenyl group), — (CO) OH or — (CO) OT ² (Wherein T ² represents an alkyl group having 1 to 4 carbon atoms). The alkyl group may be interrupted by one or more of -O-. ], — (CH ₂ CH ₂ O) _n —H [wherein n represents an integer of 1 to 20. ], An alkanoyl group having 2 to 8 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms, a cyclohexyl group, a phenyl group [the phenyl group is a halogen atom, an alkyl having 1 to 12 carbon atoms] Group or an alkoxy group having 1 to 4 carbon atoms may be substituted. ], - Ph-T ³ [wherein, Ph represents a phenyl group. T ³ represents an alkyl group having 1 to ³ carbon atoms. _{^{], - SiT 4 r Ph 3}} -r [ wherein, T ⁴ represents an alkyl group having 1 to 8 carbon atoms. Ph represents a phenyl group. r represents an integer of 1 to 3. ] Or the formula (V).

In formula (V), R ¹ and R ² represent the same meaning as described above.
M ¹ is a direct bond, an alkyleneoxy group having 1 to 12 carbon atoms [the alkyleneoxy group may be interrupted by 1 to 5 —O—, —S— and / or —NR ¹⁰ —. Or an oxyalkylene group having 1 to 12 carbon atoms [the oxyalkylene group may be interrupted by 1 to 5 —O—, —S— and / or —NR ¹⁰ —. ].

R ⁹ is a hydrogen atom, a methyl group, an alkyl group having 2 to 12 carbon atoms [the alkyl group is —OH, —SH, a cyano group, an alkoxy group having 1 to 4 carbon atoms, an alkeneoxy having 3 to 6 carbon atoms; _{groups, -OCH 2 CH 2 CN, -OCH} 2 CH 2 (CO) O-T 5 ( wherein, T ⁵ represents an alkyl group having 1 to 4 carbon atoms.), - O (CO) -T 6 ( In the formula, T ⁶ represents an alkyl group having 1 to 4 carbon atoms.), —O (CO) —Ph (wherein Ph represents a phenyl group), — (CO) OH or — (CO) O -T ⁷ (wherein T ⁷ represents an alkyl group having 1 to 4 carbon atoms) may be substituted. The alkyl group may be interrupted by one or more of -O- or -S-. ], A C3-C12 alkenyl group, a cyclohexyl group, a phenyl group [this phenyl group may be substituted with a halogen atom, a C1-C12 alkyl group or a C1-C4 alkoxy group. ] Or formula (VI).

In formula (VI), R ¹ and R ² represent the same meaning as described above.
M ² represents a direct bond or —T ¹⁴ —S— [wherein T ¹⁴ represents an alkylene group having 1 to 12 carbon atoms (the alkylene group includes 1 to 5 —O—, —S—, and / or Or may be interrupted by -NR ^10- ). ].

R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, -T ⁹ -O-T ¹⁰ [wherein T ⁹ is carbon The alkylene group of number 1-6 is represented. T ¹⁰ represents an alkyl group having 1 to 6 carbon atoms. ], An alkenyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenyl group [the phenyl group is substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. May be. ], An alkanoyl group having 2 to 3 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms or a benzoyl group.
When R ¹⁰ and R ¹¹ are bonded to the same nitrogen atom, they are taken together to form an alkylene group having 2 to 6 carbon atoms [the alkylene group is interrupted by —O— or —NR ⁸ —, and / or It may be substituted with a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkanoyloxy group having 2 to 4 carbon atoms, or a benzoyloxy group. ].
When R ¹⁰ is a hydrogen atom, R ¹¹ may be the formula (VII).

In formula (VII), R ¹ and R ² represent the same meaning as described above.
M ³ is a direct bond, piperazino group or —T ¹⁴ —NH— [wherein T ¹⁴ is an alkylene group having 1 to 12 carbon atoms (the alkylene group is 1 to 5 —O—, —S— , and / or -NR ¹⁰ -. which may be interrupted by) represents an. ].

R ¹² represents an alkoxycarbonyl group having 2 to 12 carbon atoms [the alkoxycarbonyl group may be interrupted by one or more of —O— and / or optionally substituted by one or more of hydroxyl groups. ], Phenoxycarbonyl group [wherein phenoxycarbonyl group, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a phenyl group, optionally substituted by one or more OR ⁸ or NR ¹⁰ R ^11. ], A cycloalkyl group having 5-8 carbon atoms, -CONR ¹⁰ R ^11, a cyano group, a phenyl group [wherein the phenyl group may be substituted by SR ^9, carbon of the phenyl ring with R ¹³ to R ¹⁵ By building a bond to the atom, via R ⁹ without one hydrogen atom (however, when forming a ring structure, R ⁹ is not a hydrogen atom or a cyano group), Member rings may be formed. ].
Here, when at least one of R ^{13 to} R ¹⁵ is —SR ⁹ , R ¹² represents a methyl group or an alkyl group having 2 to 12 carbon atoms [the alkyl group is a halogen atom, —OH, — It may be substituted by one or more of OR ² , phenyl group, halogenated phenyl group or SR ⁹ substituted phenyl group, or may be interrupted by —O— and / or —NH (CO) —. ].

R ^{13 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group [the phenyl group is —OR ⁸ , —SR ⁹ and — It may be substituted with at least one group selected from the group consisting of NR ¹⁰ R ¹¹ . ], A benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms [the alkoxycarbonyl group is interrupted by one or more of -O-, and / or one of hydroxyl groups] It may be substituted by more than one. ], Phenoxycarbonyl group, —OR ⁸ , —SR ⁹ , —SOR ⁹ , —SO ₂ R ⁹ or —NR ¹⁰ R ¹¹ [wherein —OR ⁸ , —SR ⁹ and —NR ¹⁰ R ¹¹ represent R ³ formation and one of the carbon atoms of the substituent or the phenyl ring of the phenyl rings present, a 5- or 6-membered ring via a single group formed by removing a hydrogen atom of R ⁸ to R ¹¹ as to R ⁷ May be. However, when forming a ring, R < ⁸ > -R < ¹¹ > is not a hydrogen atom. ]. However, at least one of R ^{13 to} R ¹⁵ represents —OR ⁸ , —SR ⁹ or —NR ¹⁰ R ¹¹ .

X is an alkylene group having 1 to 12 carbon atoms, cyclohexylene group, phenylene group,-(CO) O-T ¹² -O (CO)-[wherein T ¹² represents an alkylene group having 2 to 12 carbon atoms. . ], - (CO) O- ( CH 2 CH 2 O) n - (CO) - [ wherein, n represents an integer of 1 to 20. ], Or ^{- (CO) -T 13 - (} CO) - [ wherein, T ¹³ represents a] represents an alkylene group having 2 to 12 carbon atoms. ]

Among the above compounds, in the formulas (I) and (III), compounds in which R ³ , R ⁶ and R ⁷ represent a hydrogen atom are preferable, R ¹ represents an n-hexyl group, and R ² represents a benzoyl group. And a compound in which R ⁵ represents a phenylthio group is more preferable.

As a photoinitiator (D) used for the black photosensitive resin composition of this invention, in addition to the compound of said Formula (I)-(IV), you may use a different photoinitiator simultaneously. These compounds are not particularly limited as long as they are compounds capable of initiating addition polymerization of compounds having an ethylenically unsaturated bond, and include acetophenone photopolymerization initiators and benzoin photopolymerization initiators. Benzophenone photopolymerization initiators, thioxanthone photopolymerization initiators, triazine photopolymerization initiators, oxadiazole photopolymerization initiators, and the like can be used.
Examples of the acetophenone photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, and 2-hydroxy-2-methyl-1- [4. -(2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2- And oligomers of dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one.
Examples of the benzoin photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
Examples of the benzophenone photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.
Examples of the thioxanthone photopolymerization initiator include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
Examples of the triazine photopolymerization initiator include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p -Dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6- Bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl)- 4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2- Toxiethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl -S-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6- Methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2 -(4,7 Dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2 -(4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [PN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl ] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN- Ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s- Triazine, 4- (p-N-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6 -Di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-tri 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2 , 6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N- (Ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di ( Trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro- p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) aminophenyl] -2 , 6-Di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4 -[M-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) ) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2, 6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro Til) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN- Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- Such as o- Fluorochemicals -p-N-chloroethyl aminophenyl) -2,6-di (trichloromethyl) -s-triazine.
Examples of the oxadiazole-based photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-butoxystyryl) -1,3 4-oxadiazole, 2-trichloromethyl-5- (p-hydroxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-chlorostyryl) -1,3,4 Oxadiazole, 2-trichloromethyl-5- (p-methoxyphenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-butoxyphenyl) -1, , 4-oxadiazole, 2-trichloromethyl-5- (2-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (β- (2-benzofuryl) vinyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (β- (6-methoxy-2-benzofuryl) vinyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (2- And benzofuryl) -1,3,4-oxadiazole.
Examples of the photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 '-Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like can also be used.
Among the above photopolymerization initiators, benzophenone photopolymerization initiator, acetophenone photopolymerization initiator, triazine photopolymerization initiator having a trichloromethyl group introduced therein, and oxadiazole type having a trichloromethyl group introduced therein A photopolymerization initiator is preferably used.
Examples of the benzophenone photopolymerization initiator and the acetophenone photopolymerization initiator include those described above.
Examples of the triazine photopolymerization initiator into which the trichloromethyl group is introduced include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro) Methyl) -6 [2- (4-Diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl]- 1,3,5-triazine and the like can be mentioned.
Examples of the oxadiazole photopolymerization initiator into which the trichloromethyl group is introduced include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- ( p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p- Butoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (β- (2-benzofuryl) vinyl) -1,3,4-oxadiazole, and the like.

The black photosensitive resin composition of the present invention may contain a photopolymerization initiation aid. Examples of the photopolymerization initiation assistant include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoate. 2-ethylhexyl acid, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 9, Examples include 10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. Among these, benzophenone photopolymerization initiation assistants such as 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferably used. These photopolymerization initiation assistants can be used alone or in combination of two or more.
When using the said photoinitiator adjuvant, the usage-amount is with respect to 1 mol of photoinitiators, Preferably it is 10 mol or less, Preferably they are 0.01 mol or more and 5 mol or less.

  The total use amount of the photopolymerization initiator and the photopolymerization initiation assistant in the black photosensitive resin composition of the present invention is usually 1% or more and 50% or less by mass fraction with respect to the solid content of the black photosensitive resin composition. Preferably they are 3% or more and 30% or less, More preferably, they are 3% or more and 15% or less.

  The black photosensitive resin composition of the present invention includes additives such as thermal polymerization inhibitors, fillers, polymer compounds other than binder resins, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and aggregation inhibitors. May be contained.

  The thermal polymerization inhibitor is, for example, that during storage of the black photosensitive resin composition, (C) a compound having one or more ethylenically unsaturated bonds and capable of addition polymerization starts thermal polymerization. It may be contained to prevent it. Examples of the thermal polymerization inhibitor include haloid quinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like. When the thermal polymerization inhibitor is contained, the content is usually about 0.01% or more and 5% or less in terms of mass fraction with respect to the total amount of the black photosensitive resin composition.

  Examples of the filler include glass and alumina.

  Examples of the polymer compound other than the binder resin include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

  The surfactant may be any of a nonionic surfactant, a cationic surfactant, and an anionic surfactant.

  Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

  Examples of the antioxidant include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and the like.

  Examples of the ultraviolet absorber include 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like.

  Examples of the aggregation preventing agent include sodium polyacrylate.

  The black photosensitive resin composition of the present invention may contain an organic carboxylic acid, an organic amine compound, and the like.

Examples of the organic carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid,
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Aliphatic dicarboxylic acids such as citraconic acid,
Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid, aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid,
Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melophanoic acid, pyromellitic acid,
Organic carbons having a molecular weight of 1000 or less, such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umberic acid An acid etc. are mentioned.

As the organic amine compound, an organic amine compound having a molecular weight of 1000 or less is usually used. For example, n-propylamine, isopropylamine, n-butylamine, isobutylamine, t-butylamine, n-pentylamine, n-hexylamine. N-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, o-methylcyclohexylamine, m-methylcyclohexylamine, p-methylcyclohexylamine Mono (cyclo) alkylamines such as o-ethylcyclohexylamine, m-ethylcyclohexylamine, p-ethylcyclohexylamine;
Methyl ethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-t-butylamine, di-n-pentyl Di (cyclo) alkylamines such as amine, di-n-hexylamine, methyl cyclohexylamine, ethyl cyclohexylamine, dicyclohexylamine;
Dimethyl ethylamine, methyl diethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyl di-n-propylamine, ethyl di-n-propylamine, tri-n-propylamine, tri Isopropylamine, tri-n-butylamine, triisobutylamine, tri-t-butylamine, tri-n-pentylamine, tri-n-hexylamine, dimethyl cyclohexylamine, diethyl cyclohexylamine, methyl dicyclohexylamine, ethyl Tri (cyclo) alkylamines such as dicyclohexylamine and tricyclohexylamine;
2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino- Mono (cyclo) alkanolamines such as 1-cyclohexanol;
Diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine, di (4-cyclohexanol) amine and the like (Cyclo) alkanolamines;
Triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine, tri (4-cyclohexanol) amine Tri (cyclo) alkanolamines such as;
3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1, 2-cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol Amino (cyclo) alkanediols such as 2-diethylamino-1,3-propanediol;
1-aminocyclopentanemethanol, 4-aminocyclopentanemethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4- Amino group-containing cycloalkanemethanols such as diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Examples thereof include aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid.
Moreover, for example, a compound in which an amino group is directly bonded to a phenyl group, a compound in which an amino group is bonded to a phenyl group via a carbon chain, and the like can be given.
Examples of the compound in which the amino group is directly bonded to the phenyl group include aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, p-isopropylaniline, p Aromatic amines such as n-butylaniline, pt-butylaniline, 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline Kind;
aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;
Examples include aminobenzoic acids (derivatives) such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, and p-diethylaminobenzoic acid.

  When using the said organic carboxylic acid and an organic amine compound, it is used individually or in mixture of 2 or more types, respectively. When the organic carboxylic acid or organic amine compound is used, its content in the black photosensitive resin composition is usually 0.001% or more and 15% or less, preferably by mass fraction with respect to the black photosensitive resin composition. Is 0.01% or more and 10% or less.

The black photosensitive resin composition is usually applied on the substrate (2) in a state diluted with a solvent (FIG. 2 (a)). Examples of the solvent include esters, ethers, ketones, aromatic hydrocarbons and the like.
Esters include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate , Methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-metho Methyl cypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutane Examples include methyl acid and ethyl 2-oxobutanoate.
Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, Examples include propylene glycol ethyl ether acetate and propylene glycol propyl ether acetate.
Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Examples of aromatic hydrocarbons include toluene and xylene.

  Among the above solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethylcarbi Tall acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used.

  These solvents may be used alone or in admixture of two or more. The amount of the solvent used is selected so that the solid content in the black photosensitive resin composition is usually in the range of 2% to 50% in terms of mass fraction.

The black photosensitive resin composition is formed on the substrate (2) by a normal coating method such as a spin coating method (spin coating method), a slit coating method, a slit & spin coating method, a casting method, or a roll coating method. Can be applied.
As the substrate (2), for example, a resin substrate such as a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a polyimide substrate can be used in addition to a glass substrate and a silicon substrate. The substrate may be subjected to a pretreatment such as a chemical treatment with a chemical such as a silane coupling agent, a plasma treatment, an ion plating treatment, a sputtering treatment, a gas phase reaction treatment, or a vacuum deposition treatment.
The black photosensitive resin composition layer (1) can be formed on the substrate by coating the black photosensitive resin composition on the substrate (2) and then drying to evaporate the solvent (FIG. 2 (a)). )). The layer is a layer composed of a solid content of the black photosensitive resin composition, and the thickness thereof is usually 0.1 μm to 10 μm, preferably 0.2 μm to 5.0 μm, more preferably 0.2 μm to 3.0 μm. It is.
Next, the black photosensitive resin composition layer (1) is irradiated with the light beam (4) through the photomask (3) (FIG. 2 (b)).
The photomask (3) has a light shielding layer (32) on the surface of a glass plate (31), for example. The light ray (4) is shielded by the light shielding layer. The portion of the glass plate where the light shielding layer is not provided is the light transmitting portion (33), and the light passes through the light transmitting portion and is irradiated onto the black photosensitive resin composition layer (1). (1) is exposed according to the pattern of the translucent portion.
As the light beam (4), ultraviolet rays such as g-line (wavelength 436 nm) and i-line (wavelength 365 nm) are usually used. The light beam is preferably collimated and applied to the black photosensitive resin composition layer (1), and is usually applied via a mask aligner (not shown). According to the forming method of the present invention, since the colored pattern is formed with high resolution, for example, a colored pattern having a width of about 20 μm or less, further about 10 μm or less, and particularly 5 μm or less can be easily and stably formed. .
The amount of light irradiation is the content of the black colorant (A) used, the type and content of the binder resin (B), the compound (C) having at least one ethylenically unsaturated bond and capable of addition polymerization. It is appropriately selected according to the type and content, the type and content of the photopolymerization initiator (D), and the like.
After exposure, development is performed (FIG. 2 (c)). For development, the black photosensitive resin composition layer (1) after exposure may be brought into contact with the developer. By coming into contact with the developer, the light non-irradiated region (11) that has not been irradiated with light in the black photosensitive resin composition layer is dissolved in the developer.
As the developer, for example, an alkaline aqueous solution can be used. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline. An aqueous solution of a water-soluble alkaline compound such as pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is used, and its concentration is usually 0. It is about 001% to 10%, preferably about 0.01% to 1%. The alkaline aqueous solution may contain a water-soluble organic solvent such as methanol and ethanol, a surfactant, and the like. An organic solvent can also be used as the developer. For example, the same organic solvents as described above may be used in appropriate combination as a solvent used for diluting the black photosensitive resin composition.
The development method is not particularly limited, and for example, development can be performed by a method such as a dip development method (immersion development method), a shower development method, a spray development method, a paddle development method (a liquid development method). The development temperature is usually in the range of 10 ° C. to 40 ° C., and the development time is usually 10 seconds to 300 seconds.
By the development, the light non-irradiated region (11) in the black photosensitive resin composition layer that has not been irradiated with the light is dissolved in the developer and removed. On the other hand, the light-irradiated region (12) irradiated with the light remains to form the colored pattern (5).
A colored pattern (5) is obtained by drying after development (FIG. 2 (c)). When an alkaline aqueous solution is used as the developer, it is usually dried after washing with water after development. You may heat-process after drying.
In this way, a colored pattern is obtained. However, according to the forming method of the present invention, since the development margin is wide, the yield can be improved and the resolution is good, so even a fine colored pattern can be easily formed. be able to.
The obtained colored pattern is useful as a black matrix.

  While the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and further includes meanings equivalent to the description of the claims and all modifications within the scope. EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.

Example 1
[Preparation of black photosensitive resin composition 1]
(A) Black colorant [mixture of 198 parts by mass of black pigment (CI Pigment Black 7) and 45.5 parts by mass of dispersant] 184 parts by mass,
(B) Binder resin [300 parts by mass of the compound represented by the formula (XIV), 50 parts by mass of biphenyltetracarboxylic dianhydride, 50 parts by mass of tetrahydrophthalic anhydride are described in JP-A-8-278630. Polycarboxylic acid resin obtained by reacting in the same manner as in the above method] 100 parts by mass,

Compound (C) [dipentaerythritol hexaacrylate] having an ethylenically unsaturated bond and capable of addition polymerization, 33 parts by mass,
Photopolymerization initiator (D) [compound represented by formula (XV)] 14.8 parts by mass and

1178 parts by mass of the solvent (E) [propylene glycol monomethyl ether acetate] was mixed to obtain a black photosensitive resin composition 1.

[Formation of black photosensitive resin composition layer]
The black photosensitive resin composition 1 is applied to the surface of a glass substrate (“# 1737” manufactured by Corning) (2) by spin coating, heated at 100 ° C. for 3 minutes and dried to obtain a black photosensitive resin. The composition layer (1) was formed on the substrate (2). The thickness of the black photosensitive resin composition layer after drying was 1.0 μm.

[Black pattern formation (resolution evaluation)]
The substrate (2) on which the black photosensitive resin composition layer (1) was formed as described above was irradiated with ultraviolet rays (irradiation amount was 200 mJ / cm ² ) through a photomask (3) with an ultrahigh pressure mercury lamp, and was exposed. As the photomask (3), linear (line and space) colored patterns (2) having a line width of 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm and 100 μm are formed. A photomask was used.
The black photosensitive resin composition layer after the exposure was developed by immersing it in a developer (an aqueous solution containing 0.05% by weight of potassium hydroxide and containing a nonionic surfactant, 23 ° C.) for 90 seconds.
After the development, it was washed with water and heated at 230 ° C. for 20 minutes to form a black colored pattern (black matrix) on the substrate (2). When this black matrix was observed with an optical microscope, a colored pattern having a line width of 4 μm was formed with good reproducibility.

[Black pattern formation (evaluation of development margin)]
The black photosensitive resin composition layer exposed on the black photosensitive resin composition layer formed on the substrate in the same manner as described above is developed by immersing in the same developer as used above, and a development time of 10 μm is reproduced. When the width was observed, a 10 μm pattern was formed with good reproducibility between 40 seconds and 120 seconds, that is, with a development margin of 80 seconds.

[Evaluation of sensitivity]
Operate in the same manner as above except that exposure is performed using a mask pattern in which the light transmittance of the light-shielding layer changes stepwise as the mask pattern, and the minimum amount of light irradiation (sensitivity required for pattern formation) )
The sensitivity obtained was as high as 80 mJ / cm ² .

Example 2
[Preparation of black photosensitive resin composition 2 and formation of black photosensitive resin composition layer]
Instead of the binder resin used in Example 1, after reacting 463 parts by mass of the compound represented by the formula (XVI) with 87 parts by mass of itaconic acid, 48 parts by mass of acrylic acid was added to react. In addition, a black photosensitive resin composition 2 was obtained in the same manner as in Example 1 except that 33 parts by mass of a polycarboxylic acid resin obtained by reacting 102 parts by mass of tetrahydrophthalic anhydride was used. A black photosensitive resin composition layer (thickness: 1.0 μm) was formed.

[Evaluation]
Except using the board | substrate with which the black photosensitive resin composition layer obtained above was used instead of the board | substrate (2) with which the black photosensitive resin composition layer (1) obtained in Example 1 was formed, it is Example. In the same manner as in No. 1, the resolution, development margin and sensitivity were evaluated.
The results are shown in Table 1.

Example 3
[Preparation of Black Photosensitive Resin Composition 3 and Formation of Black Photosensitive Resin Composition Layer]
Instead of using the photopolymerization initiator used in Example 1, a mixture of 7.4 parts by mass of the compound represented by the formula (XV) and 7.4 parts by mass of the compound represented by the formula (XVII) was used. By operating in the same manner as in Example 1, a black photosensitive resin composition was obtained, and a black photosensitive resin composition layer (thickness: 1.0 μm) was formed.

[Evaluation]
Except using the board | substrate with which the black photosensitive resin composition layer obtained above was used instead of the board | substrate (2) with which the black photosensitive resin composition layer (1) obtained in Example 2 was formed, Example In the same manner as in No. 2, the resolution, development margin and sensitivity were evaluated.
The results are shown in Table 1.

Example 4
[Preparation of Black Photosensitive Resin Composition 4 and Formation of Black Photosensitive Resin Composition Layer]
In place of the binder resin used in Example 1, the compound represented by the binder resin [formula (XVIII) (softening point, epoxy equivalent and hydrolyzable chlorine content are 74 ° C., 336 g / eq and 230 ppm, respectively). And 98) parts by mass

The reaction was conducted in the same manner as in Example 1 except that 21 parts by mass of acrylic acid was added and reacted, and then polycarboxylic acid resin obtained by further reacting 7.2 parts by mass of tetrahydrophthalic anhydride] 33 parts by mass. Then, a black photosensitive resin composition 4 was obtained, and a black photosensitive resin composition layer (thickness: 1.0 μm) was formed.

[Evaluation]
Except using the board | substrate with which the black photosensitive resin composition layer obtained above was used instead of the board | substrate (2) with which the black photosensitive resin composition layer (1) obtained in Example 1 was formed, it is Example. In the same manner as in No. 1, the resolution, development margin and sensitivity were evaluated.
The results are shown in Table 1.

Example 5
[Preparation of Black Photosensitive Resin Composition 3 and Formation of Black Photosensitive Resin Composition Layer]
Instead of the photopolymerization initiator used in Example 1, a mixture of 11.1 parts by mass of the compound represented by the formula (XV) and 3.7 parts by mass of the compound represented by the formula (XIX) was used. By operating in the same manner as in Example 1, a black photosensitive resin composition was obtained, and a black photosensitive resin composition layer (thickness 1.0 μm) was formed.

[Evaluation]
Except using the board | substrate with which the black photosensitive resin composition layer obtained above was used instead of the board | substrate (2) with which the black photosensitive resin composition layer (1) obtained in Example 2 was formed, Example In the same manner as in No. 2, the resolution, development margin and sensitivity were evaluated.
The results are shown in Table 1.

Example 6
[Preparation of Black Photosensitive Resin Composition 3 and Formation of Black Photosensitive Resin Composition Layer]
Instead of the photopolymerization initiator used in Example 1, 7.4 parts by mass of the compound represented by the formula (XV), 3.7 parts by mass of the compound represented by the formula (XIX),

And a black photosensitive resin composition (thickness) obtained in the same manner as in Example 1 except that a mixture of 3.7 parts by mass of the compound represented by the formula (XX) is used. 1.0 μm) was formed.

[Evaluation]
Except using the board | substrate with which the black photosensitive resin composition layer obtained above was used instead of the board | substrate (2) with which the black photosensitive resin composition layer (1) obtained in Example 2 was formed, Example In the same manner as in No. 2, the resolution, development margin and sensitivity were evaluated.
The results are shown in Table 1.

Comparative Example 1
[Preparation of Black Photosensitive Resin Composition 5 and Formation of Black Photosensitive Resin Composition Layer]
The black photosensitive resin composition 4 was operated in the same manner as in Example 1 except that 14.8 parts by mass of the compound represented by the formula (XVII) was used instead of the photopolymerization initiator used in Example 1. To obtain a black photosensitive resin composition layer (thickness: 1.0 μm).

[Evaluation]
Except using the board | substrate with which the black photosensitive resin composition layer obtained above was used instead of the board | substrate (2) with which the black photosensitive resin composition layer (1) obtained in Example 1 was formed, it is Example. In the same manner as in No. 1, the resolution, development margin and sensitivity were evaluated. The results are shown in Table 1.

Comparative Example 2
[Preparation of Black Photosensitive Resin Composition 6 and Formation of Black Photosensitive Resin Composition Layer]
Instead of the binder resin used in Example 1, a copolymer of benzyl methacrylate and methacrylic acid [the content of benzyl methacrylate units is 65% in terms of mole fraction, and the content of methacrylic acid units is 35% in terms of mole fraction. The polystyrene-reduced weight average molecular weight is 13,000]. 80 parts by weight is used, and the black photosensitive resin composition 5 is operated in the same manner as in Example 1 except that the amount of dipentaerythritol hexaacrylate is 53 parts by weight. To obtain a black photosensitive resin composition layer (thickness: 1.0 μm).

[Evaluation]
Except using the board | substrate with which the black photosensitive resin composition layer obtained above was used instead of the board | substrate (2) with which the black photosensitive resin composition layer (1) obtained in Example 1 was formed, it is Example. In the same manner as in No. 1, the resolution, development margin and sensitivity were evaluated. The results are shown in Table 1.

  According to the black photosensitive resin composition of the present invention, it is possible to form a colored pattern, particularly a black matrix, with good resolution, development margin and sensitivity, and to improve the yield of the color filter and thus the liquid crystal display device.

It is a schematic diagram which shows an example of a color filter partially. It is a schematic diagram which shows the process of forming a coloring pattern on a board | substrate using a coloring photosensitive resin composition. It is a schematic diagram which shows the process of forming a coloring pattern on a board | substrate using a coloring photosensitive resin composition. It is a schematic diagram which shows the process of forming a coloring pattern on a board | substrate using a coloring photosensitive resin composition.

Explanation of symbols

1: Colored photosensitive resin composition layer 11: Non-irradiated region
12: Light irradiation area 2: Substrate 3: Photomask 31: Glass plate
32: Light shielding layer
33: Translucent part 4: Light beam 5: Colored pattern 5R: Red pixel
5G: Green pixel
5B: Blue pixel
5BM: Black matrix 6: Color filter

Claims (11)

Black photosensitive resin composition containing black colorant (A), binder resin (B), compound (C) having an ethylenically unsaturated bond and capable of addition polymerization, and at least one photopolymerization initiator (D) A thing,
A polycarboxylic acid obtained by reacting an unsaturated monocarboxylic acid with a reaction product of a compound having two or more epoxy groups and a polybasic carboxylic acid, and further reacting an anhydride of the polybasic carboxylic acid with the binder resin (B). Acid resin (b1 and selected from the group consisting of polycarboxylic acid resin (b2) obtained by reacting unsaturated monocarboxylic acid with a compound having two or more epoxy groups and further reacting with anhydride of polybasic carboxylic acid At least one polycarboxylic acid resin, and the photopolymerization initiator (D) is a photopolymerization initiator containing an oxime compound , and further a triazine photopolymerization initiator, a benzophenone photopolymerization initiator, black photosensitive resin composition containing at least one selected from the group consisting of benzophenone photopolymerization initiation aid and acetophenone photopolymerization initiator . The black photosensitive resin composition according to claim 1, wherein the oxime compound contains at least one compound selected from the group consisting of compounds represented by formulas (I) to (IV).

[In formulas (I) to (IV), R ^{1 to} R ¹⁵ each have the following meaning.
R ¹ represents a phenyl group [the phenyl group is at least one selected from the group consisting of a halogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, —OR ⁸ , —SR ⁹ and —NR ¹⁰ R ¹¹ . It may be substituted by a group. ], A methyl group, an alkyl group having 2 to 20 carbon atoms [the alkyl group may be interrupted by one or more of -O-, and / or substituted by one or more of hydroxyl groups. ], A cycloalkyl group having 5-8 carbon atoms, alkanoyl group having 2 to 20 carbon atoms, a benzoyl group [wherein the benzoyl group is an alkyl group, a phenyl group having 1 to 6 carbon atoms, -OR ^8, -SR ⁹ and - It may be substituted with at least one selected from the group consisting of NR ¹⁰ R ¹¹ . ], An alkoxycarbonyl group having 2 to 12 carbon atoms [the alkoxycarbonyl group may be interrupted by one or more of —O— and / or substituted by one or more of hydroxyl groups. ], A phenoxycarbonyl group [the phenoxycarbonyl group is composed of at least one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, a phenyl group, —OR ⁸ , —SR ⁹ and —NR ¹⁰ R ^11. May be substituted. ], - CONR ¹⁰ R ¹¹ group, a cyano group, a nitro group, halogenated alkyl group [the halogen atom of from 1 to 4 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. ], - ^{SO-Z 1} [wherein, ^{Z 1} represents an alkyl group having 1 to 6 carbon atoms. ], - SO ₂ -Z ¹ [wherein, ^{Z 1} are as defined above. ^{], - Z 2 -SO-Z} 3 [ wherein, Z ² represents an alkylene group having 1 to 12 carbon atoms, Z ³ represents an aryl group having 6 to 12 carbon atoms. ], -Z ⁴ -SO ₂ -Z ³ [wherein Z ⁴ represents an alkylene group having 1 to 12 carbon atoms, and Z ³ represents the same meaning as described above.] ], - in SO ₂ ^{O-Z 5} [wherein, ^{Z 5} represents an aryl group having 6 to 10 carbon atoms. Or a diphenyl-phosphinoyl group;
R ² represents an alkanoyl group having 2 to 12 carbon atoms [the alkanoyl group may be substituted with one or more halogen atoms or cyano groups. ], An alkenoyl group having 4 to 6 carbon atoms [wherein the double bond of the alkenoyl group is not conjugated with the carbonyl group. A benzoyl group [the benzoyl group is substituted by at least one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, —OR ⁸ , —SR ⁹ and —NR ¹⁰ R ^11. It may be. ], A C2-C6 alkoxycarbonyl group or a phenoxycarbonyl group [this phenoxycarbonyl group may be substituted by a C1-C6 alkyl group or a halogen atom. ];
R ^{3 to} R ⁷ are each independently a hydrogen atom, a halogen atom, a cyclopentyl group, a cyclohexyl group, or a phenyl group [the phenyl group is selected from the group consisting of —OR ⁸ , —SR ⁹ and —NR ¹⁰ R ^11. Optionally substituted with at least one group. ], A benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms [wherein the alkoxycarbonyl group is interrupted by one or more of -O-, and / or It may be substituted by one or more of the hydroxyl groups. ], Phenoxycarbonyl group, —OR ⁸ , —SR ⁹ , —SOR ⁹ , —SO ₂ R ⁹ or —NR ¹⁰ R ¹¹ [wherein —OR ⁸ , —SR ⁹ and —NR ¹⁰ R ¹¹ represent R ³ formation and one of the carbon atoms of the substituent or the phenyl ring of the phenyl rings present, a 5- or 6-membered ring via a single group formed by removing a hydrogen atom of R ⁸ to R ¹¹ as to R ⁷ May be. However, when forming a ring, R < ⁸ > -R < ¹¹ > is not a hydrogen atom. Wherein at least one of R ^{3 to} R ⁷ is selected from the group consisting of —OR ⁸ , —SR ⁹ and —NR ¹⁰ R ¹¹ ;
R ⁸ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms [the alkyl group is —OH, —SH, a cyano group, an alkoxy group having 1 to 4 carbon atoms, an alkeneoxy group having 3 to 6 carbon atoms, — _{OCH 2 CH 2 CN, -OCH 2} CH 2 (CO) O-T 1 ( where T ¹ represents an alkyl group having 1 to 4 carbon atoms.), - O (CO) -Z 6 ( wherein, Z ⁶ represents an alkyl group having 1 to 4 carbon atoms.), —O (CO) —Ph (wherein Ph represents a phenyl group), — (CO) OH or — (CO) OT ² (Wherein T ² represents an alkyl group having 1 to 4 carbon atoms), and the alkyl group may be interrupted by one or more of —O—. ], — (CH ₂ CH ₂ O) _n —H [wherein n represents an integer of 1 to 20. ], An alkanoyl group having 2 to 8 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms, a cyclohexyl group, a phenyl group [the phenyl group is a halogen atom, an alkyl having 1 to 12 carbon atoms] Group or an alkoxy group having 1 to 4 carbon atoms may be substituted. ], - Ph-T ³ [wherein, Ph represents a phenyl group. T ³ represents an alkyl group having 1 to ³ carbon atoms. ], - SiT in ⁴ _r Ph _3-r [wherein, T ⁴ represents an alkyl group having 1 to 8 carbon atoms, Ph represents a phenyl group, r is represents an integer of 1 to 3. ] Or formula (V),

In formula (V), R ¹ and R ² represent the same meaning as described above, M ¹ represents a single bond, an alkyleneoxy group having 1 to 12 carbon atoms [the alkyleneoxy group is 1 to 5 —O— , -S- and / or -NR ¹⁰ - it may be interrupted by. Or an oxyalkylene group having 1 to 12 carbon atoms [the oxyalkylene group may be interrupted by 1 to 5 —O—, —S— and / or —NR ¹⁰ —. ];
R ⁹ is a hydrogen atom, a methyl group, an alkyl group having 2 to 12 carbon atoms [the alkyl group is —OH, —SH, a cyano group, an alkoxy group having 1 to 4 carbon atoms, an alkeneoxy having 3 to 6 carbon atoms; _{groups, -OCH 2 CH 2 CN, -OCH} 2 CH 2 (CO) O-T 5 ( wherein, T ⁵ represents an alkyl group having 1 to 4 carbon atoms.), - O (CO) -T 6 ( In the formula, T ⁶ represents an alkyl group having 1 to 4 carbon atoms.), —O (CO) —Ph (wherein Ph represents a phenyl group), — (CO) OH or — (CO) O -T ⁷ (wherein T ⁷ represents an alkyl group having 1 to 4 carbon atoms) may be substituted. The alkyl group may be interrupted by one or more of -O- or -S-. ], A C3-C12 alkenyl group, a cyclohexyl group, a phenyl group [this phenyl group may be substituted with a halogen atom, a C1-C12 alkyl group or a C1-C4 alkoxy group. ] Or formula (VI)

In formula (VI), R ¹ and R ² represent the same meaning as described above, M ² represents a single bond or —T ¹⁴ —S— [wherein T ¹⁴ represents an alkylene group having 1 to 12 carbon atoms (including An alkylene group may be interrupted by 1 to 5 —O—, —S—, and / or —NR ¹⁰ —. ];
R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, -T ⁹ -O-T ¹⁰ [wherein T ⁹ is carbon represents an alkylene group having 1 to 6, T ¹⁰ represents an alkyl group having 1 to 6 carbon atoms. ], An alkenyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenyl group [the phenyl group is substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. May be. Represents an alkanoyl group having 2 to 3 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms or a benzoyl group, and when R ¹⁰ and R ¹¹ are bonded to the same nitrogen atom, -6 alkylene group [the alkylene group is interrupted by -O- or -NR ^8- and / or a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkanoyloxy group having 2 to 4 carbon atoms or a benzoyloxy group May be substituted. And when R ¹⁰ is a hydrogen atom, R ¹¹ may be of formula (VII)

In formula (VII), R ¹ and R ² represent the same meaning as described above, and M ³ represents a single bond, a piperazino group or —T ¹⁴ —NH— [wherein T ¹⁴ is an alkylene having 1 to 12 carbon atoms. A group (the alkylene group may be interrupted by 1 to 5 —O—, —S—, and / or —NR ¹⁰ —). ];
R ¹² represents an alkoxycarbonyl group having 2 to 12 carbon atoms [the alkoxycarbonyl group may be interrupted by one or more of —O— and / or optionally substituted by one or more of hydroxyl groups. ], Phenoxycarbonyl group [wherein phenoxycarbonyl group, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a phenyl group, optionally substituted by one or more OR ⁸ or NR ¹⁰ R ^11. ], A cycloalkyl group having 5-8 carbon atoms, -CONR ¹⁰ R ^11, a cyano group, a phenyl group [wherein the phenyl group may be substituted by SR ^9, carbon of the phenyl ring with R ¹³ to R ¹⁵ By building a bond to the atom, via R ⁹ without one hydrogen atom (however, when forming a ring structure, R ⁹ is not a hydrogen atom or a cyano group), Member rings may be formed. In the case where at least one of R ^{13 to} R ¹⁵ is —SR ⁹ , R ¹² represents a methyl group or an alkyl group having 2 to 12 carbon atoms [the alkyl group is a halogen atom, —OH , —OR ² , a phenyl group, a halogenated phenyl group, or an SR ⁹ substituted phenyl group, or may be interrupted by —O— and / or —NH (CO) —. . ];
R ^{13 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group [the phenyl group is —OR ⁸ , —SR ⁹ and — It may be substituted with at least one group selected from the group consisting of NR ¹⁰ R ¹¹ . ], A benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms [the alkoxycarbonyl group is interrupted by one or more of -O-, and / or one of hydroxyl groups] It may be substituted by more than one. ], A phenoxycarbonyl group, —OR ⁸ , —SR ⁹ , —SOR ⁹ , —SO ₂ R ⁹ or —NR ¹⁰ R ¹¹ [wherein —OR ⁸ , —SR ⁹ and —NR ¹⁰ R ¹¹ are R ³ Forming a 5-membered or 6-membered ring through one of the above substituents of the phenyl ring existing as -R ⁷ or one of the carbon atoms of the phenyl ring and a group obtained by removing one hydrogen atom of R ⁸ -R ¹¹ However, when forming a ring, R < ⁸ > -R < ¹¹ > is not a hydrogen atom. Wherein at least one of R ^{13 to} R ¹⁵ represents —OR ⁸ , —SR ⁹ or —NR ¹⁰ R ¹¹ ;
X is an alkylene group having 1 to 12 carbon atoms, cyclohexylene group, phenylene group,-(CO) O-T ¹² -O (CO)-[wherein T ¹² represents an alkylene group having 2 to 12 carbon atoms. . ], - (CO) O- ( CH 2 CH 2 O) n - (CO) - [ wherein, n represents an integer of 1 to 20. ], Or ^{- (CO) -T 13 - (} CO) - [ wherein, T ¹³ represents a] represents an alkylene group having 2 to 12 carbon atoms. ] R ¹ is a phenyl group or an alkyl group having 2 to 8 carbon atoms; R ² is an alkanoyl group having 2 to 6 carbon atoms or a benzoyl group [the benzoyl group is an alkyl group having 1 to 6 carbon atoms; It may be substituted with at least one selected from the group consisting of halogen atoms. R ³ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom or a phenyl group [the phenyl group is a group consisting of —OR ⁸ , —SR ⁹ and —NR ¹⁰ R ^11] It may be substituted with at least one group selected from And R ⁵ is —OR ⁸ , —SR ⁹ , or —NR ¹⁰ R ^11, wherein —OR ⁸ , —SR ⁹ and —NR ¹⁰ R ¹¹ are phenyl present as R ^{3 to} R ^7. and one of the carbon atoms of the substituent or the phenyl ring of the ring, may form a 5- or 6-membered ring via a single group formed by removing a hydrogen atom of R ⁸ to R ^11. However, when forming a ring, R < ⁸ > -R < ¹¹ > is not a hydrogen atom. The black photosensitive resin composition according to claim 2. 4. The black photosensitive resin composition according to claim 2, wherein R ³ , R ⁶ and R ⁷ are all hydrogen atoms. The black photosensitive resin composition according to claim ² , wherein R ¹ is an n-hexyl group, R ² is a benzoyl group, and R ⁵ is a phenylthio group. The black photosensitive composition according to any one of claims 1 to 5 , wherein the compound having two or more epoxy groups is at least one compound selected from the group consisting of compounds represented by formula (VIII) and formula (IX). Resin composition.

[In formula (VIII), p represents an integer of 1 or more and 20 or less,
R ^{16 to} R ¹⁹ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl having 7 to 20 carbon atoms. Represents a group,
Q ^{1 to} Q ¹¹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an alkynyl group having 1 to 8 carbon atoms, or an alkyl group having 5 to 12 carbon atoms. A cycloalkyl group, an aryl group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyloxy group having 1 to 8 carbon atoms, and an alkynyloxy group having 1 to 8 carbon atoms Represents an aryloxy group having 6 to 14 carbon atoms, a nitro group, or a cyano group. ],

Wherein (IX), Q ¹² ~Q ¹⁵ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms,
R ²⁰ represents an alkylene group having 1 to 10 carbon atoms,
q represents an integer of 0 to 5;
Y represents a single bond or a divalent residue represented by any one of formulas (IX-1) to (IX-8). ]

The black photosensitive composition according to any one of claims 1 to 6 , wherein the black colorant (A) contains at least one black colorant selected from the group consisting of carbon black and coated carbon black. Colored pattern formed using the black photosensitive resin composition according to any one of claims 1-7. The colored pattern according to claim 8 , which is for a black matrix. A color filter comprising a colored pattern of claim 8 or 9, wherein. Display device comprising comprising a color filter according to claim 1 0, wherein.

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