TW201922803A - Photosensitive resin composition, cured product, black matrix and image display device - Google Patents

Abstract

Provided is a high-resistance photosensitive resin composition having a superior light blocking effect and insulating capacity. The photosensitive resin composition of the present invention comprises (a) an alkali soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, and (d) a coloring material, (c) the photopolymerization initiator comprising a photopolymerization initiator (cl) represented by the following general formula (1), and the (d) coloring material comprising a high-resistance carbon black. (In the above formula (1), R1, R2 and R3 represent, the same or different from each other, an alkyl group which may have (a) substituent(s) and the like, R4 represents an alkyl group which may have (a) substituent(s) and the like, R5 represents an alkyl group which may have (a) substituent(s) and the like, A represents oxygen atom or sulfur atom, m represents an integer from 0 to 4, n represents an integer from 0 to 4, and p represents an integer from 0 to 4. Any aromatic rings contained in the formula (1) may include a fused ring as long as the fused ring is formed by two or less rings.).

Description

Photosensitive resin composition, cured product, black matrix, and image display device

The present invention relates to a photosensitive resin composition, a cured product, a black matrix, and an image display device. In particular, the present invention relates to a photosensitive resin composition having high insulation properties and high resistance, a cured product obtained by curing the same, and an image display device having the cured product. The photosensitive resin composition of the present invention is suitable for a high-resistance black photosensitive resin composition having excellent light-shielding properties and insulation properties, particularly a photosensitive resin composition for a black matrix (hereinafter referred to as "BM"). The entire contents of the specification, scope, drawings, and abstract of Japanese Patent Application No. 2017-186138 filed with the Japan Patent Office on September 27, 2017 will be filed with Japan Patent Office on December 14, 2017. May the entire contents of the description, patent application scope, drawings and abstracts of 2017-239159, as well as the contents disclosed in the documents cited in this specification, be incorporated in part or in whole as part of the disclosure of this specification.

Color filters are usually formed on the surface of transparent substrates such as glass and plastic to form a black matrix, and then form a grid, stripe, or mosaic pattern in order to form three or more different colors of red, green, and blue. Vegetarian. The pattern size varies depending on the application of the color filter and each color, and is usually about 5 to 700 μm.

As a representative manufacturing method of a color filter, a pigment dispersion method is known today. When a color filter is manufactured by a pigment dispersion method, first, a photosensitive resin composition containing a black pigment such as carbon black is coated on a transparent substrate and then dried, and then image exposure and development are performed. BM is formed by heating and hardening at a high temperature of 200 ° C or higher. A pixel is formed by repeating the above operations for each color of red, green, and blue, and a color filter having BM and pixels is formed.

BM is usually arranged in a grid, stripe, or mosaic pattern among red, green, and blue pixels. It has the effect of improving contrast or preventing light leakage by suppressing color mixing between pixels. Therefore, BM is required to have a high light-shielding property. In addition, the edge portions of the pixels of red, green, and blue formed after the formation of the BM partially overlap with the BM, and therefore, affected by the film thickness of the BM, a step is generated at the overlapping portion. At this overlapping portion, the flatness of the pixels is impaired, unevenness of liquid crystal cell gaps or disordered liquid crystal alignment are caused, which causes a decrease in display capability. Therefore, in recent years, thinning of BM has been demanded. In order to exhibit sufficient light-shielding properties even during thinning, there is a tendency that the pigment content ratio in the photosensitive resin composition becomes higher.

Furthermore, in order to cope with various display panel methods, it is also required to increase the volume resistance of BM. For example, in Patent Document 1, as a countermeasure against display unevenness of a liquid crystal display device with a lateral electric field method, it is disclosed that an improvement effect is obtained by applying a high-resistance BM. When a BM or a light-shielding film is formed on a TFT (thin-film transistor) array substrate to prevent malfunction caused by light from the TFT element, the BM or the light-shielding film is in contact with the pixel electrode or the TFT element. Short circuit or leakage current, need to be BM or light shielding film with higher insulation.

In recent years, the design of narrow bezels that can increase the display area in displays for televisions or mobile phones has been continuously developed. It is also considered to change the wiring path or arrangement of the electrical wiring previously arranged in the frame area and arrange it in the display area. When the BM is in direct contact with the electrical wiring when the wiring path is changed, high insulation is required, that is, a high-resistance BM.

On the other hand, regarding the driving of the liquid crystal panel, in order to display a moving image that moves quickly without leaving an afterimage, the response time of the liquid crystal panel must be shortened. The shortening of the response time can be achieved by increasing the applied voltage of the driving circuit and speeding up the alignment change of the liquid crystal material. Therefore, a high-resistance BM with less leakage current than the previous applied voltage is required. Therefore, it is required to achieve further high resistance while maintaining the previous BM performance. In response to such a request, for example, Patent Document 2 discloses a method using a resin-coated carbon black, and Patent Document 3 or 4 discloses a method using a modified carbon black having a specific organic group bonded thereto. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 9-43590 [Patent Literature 2] Japanese Patent Laid-Open Publication No. 2013-195538 [Patent Literature 3] Japanese Patent Publication No. 2008-517330 [Patent Literature 4] International Publication No. 2003/076527

[Problems to be solved by the invention]

As disclosed in the aforementioned Patent Documents 2 to 4, the conventional high-resistance BM was prepared and produced with high-resistance (insulation) carbon black by surface treatment such as forming an insulating film on the surface of the conductive carbon black. (High-resistance carbon black) No research has been conducted on the benefits of other constituents in increasing the resistance. The high resistance of BM is only based on the surface treatment technology of carbon black.

The present inventors have studied the photosensitive resin composition described in Patent Documents 2 to 4, and as a result, it has been clarified that the volume resistivity of BM is about 10 ¹¹ Ω · cm (measurement voltage 10 V), which is not a sufficiently high resistance. (About 10 ¹³ Ω · cm or more). In order to achieve higher resistance, there is a method of thickening the coating treatment layer on the surface of carbon black. However, the thickening of the coating layer destroys the overall balance of the photosensitive resin composition, and the following problems occur on the performance side: (i ) Decrease in alkali-soluble component or cross-linking hardening component leads to reduction in resolution and substrate adhesion, and (ii) reduction in OD (light-shielding property) caused by reduction in amount of carbon black that can be added. Therefore, it is not only difficult to achieve high resistance of carbon black itself, but also difficult to increase resistance of BM.

It is therefore an object of the present invention to provide a high-resistance photosensitive resin composition excellent in light shielding properties and insulation properties. [Technical means to solve the problem]

In order to solve the above-mentioned problems, the present inventors also made intensive studies on components other than colorants, and found that the above-mentioned problems can be solved by containing a specific photopolymerization initiator in the photosensitive resin composition. That is, the subject matter of the present invention is as follows.

[1] A photosensitive resin composition comprising: (a) an alkali-soluble resin; (b) a photopolymerizable monomer; (c) a photopolymerization initiator; and (d) a colorant; and The (c) photopolymerization initiator contains a photopolymerization initiator (c1) represented by the following general formula (1), and the (d) colorant contains high-resistance carbon black (d1);

[Chemical 1]

(In the above formula (1), R ¹ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent; R ² represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent; R ³ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent; R ⁴ represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aromatic ring group which may have a substituent , Hydroxy or nitro, which may be bonded via a divalent linking group; R ⁵ represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and may have a substituent Aromatic ring group, halogen atom, hydroxyl group or nitro group; A represents an oxygen atom or a sulfur atom; m represents an integer of 0 to 4; n represents an integer of 0 to 4; p represents an integer of 0 to 4; The aromatic ring contained in) may contain a condensed ring, but the number of rings contained in the condensed ring is two or less). [2] The photosensitive resin composition according to [1], wherein the high-resistance carbon black (d1) contains a coated carbon black. [3] The photosensitive resin composition according to [1] or [2], wherein the volume resistivity of the high-resistance carbon black (d1) is 3 Ω · cm or more. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the (a) alkali-soluble resin contains an epoxy (meth) acrylate resin having a carboxyl group. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the optical density per film thickness is 2.5 or more.

[6] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [5]. [7] A black matrix containing a hardened substance as in [6]. [8] An image display device having a hardened body as in [6]. [Effect of the invention]

According to the present invention, it is possible to provide a high-resistance photosensitive resin composition excellent in light shielding properties and insulation properties.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist thereof. In addition, in the present invention, the "(meth) acrylic acid" means "acrylic and / or methacrylic acid", and the same applies to "(meth) acrylate" and "(meth) acrylfluorenyl".

In the present invention, the "total solid content component" means all components other than the solvent contained in the photosensitive resin composition or the following ink. In the present invention, the weight average molecular weight refers to a weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography). In the present invention, unless otherwise specified, the "amine value" means the amine value in terms of effective solid content, which is the KOH equivalent to the amount of alkali per 1 g of the solid content of the dispersant. The value represented by mass. The measurement method will be described later.

[Photosensitive resin composition] The photosensitive resin composition of the present invention is characterized in that it contains (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, and (d) For colorants, the (c) photopolymerization initiator contains a photopolymerization initiator (c1) represented by the following general formula (1), and the (d) colorant contains high-resistance carbon black (d1).

[Chemical 2]

In the formula (1), R ¹ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. R ² represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. R ³ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. R ⁴ represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aromatic cyclic group which may have a substituent, a hydroxyl group or a nitro group, and these may be bonded via a divalent linking group. R ⁵ represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, an aromatic ring group which may have a substituent, a halogen atom, a hydroxyl group, or a nitro group. A represents an oxygen atom or a sulfur atom. m represents an integer from 0 to 4. n represents an integer from 0 to 4. p represents an integer from 0 to 4. The aromatic ring contained in formula (1) may contain a condensed ring, but the number of rings contained in the condensed ring is two or less.

The photosensitive resin composition of the present invention may further contain a dispersant and a thiol, and may further include formulation ingredients such as an adhesion promoter, a coating improver, a pigment derivative, a development improver, an ultraviolet absorber, and an antioxidant. In general, each of the preparation ingredients is used in a state of being dissolved or dispersed in an organic solvent. One of the characteristics of this invention is a photosensitive resin composition, (c) The photoinitiator contains a photoinitiator (c1). First, (c) a photopolymerization initiator will be described.

<(C) Photopolymerization initiator> The (c) photopolymerization initiator of this invention contains the photopolymerization initiator (c1) represented by following General formula (1).

<Photopolymerization initiator (c1)> The photopolymerization initiator (c1) is a photopolymerization initiator represented by the following general formula (1).

[Chemical 3]

In the formula (1), R ¹ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. R ² represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. R ³ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. R ⁴ represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aromatic cyclic group which may have a substituent, a hydroxyl group or a nitro group, and these may be bonded via a divalent linking group. R ⁵ represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, an aromatic ring group which may have a substituent, a halogen atom, a hydroxyl group, or a nitro group. A represents an oxygen atom or a sulfur atom. m represents an integer from 0 to 4. n represents an integer from 0 to 4. p represents an integer from 0 to 4. The aromatic ring contained in formula (1) may contain a condensed ring, but the number of rings contained in the condensed ring is two or less.

As described above, regarding the photopolymerization initiator (c1) represented by the general formula (1), it is considered that the aromatic ring contained in formula (1) may contain a condensed ring, but the number of rings contained in the condensed ring is Two or less, that is, two or less rings, so that the jump conduction and the like derived from the photopolymerization initiator are suppressed, and even when the applied voltage is increased, the insulation becomes good. In addition, it is thought that because it has a benzofuran ring or a benzothiophene ring, it interacts with carbon black and is easily adsorbed near the surface of its particles. surface. It is thought that by this, the exposed light is effectively used before being absorbed by the carbon black, and the hardenability inside the film is improved, whereby the flow and aggregation of the carbon black particles are suppressed, and the resistance drop is easily suppressed.

(R ¹ ) In the formula (1), R ¹ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. The alkyl group in R ¹ may be linear, branched, or cyclic, or may be formed by such bonding. The number of carbon atoms of the alkyl group is not particularly limited, but it is usually 1 or more, preferably 12 or less, more preferably 6 or less, even more preferably 3 or less, and even more preferably 2 or less. When it is below the above-mentioned upper limit value, there is a tendency that the crosslinking density becomes higher. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, pentyl, isopentyl, cyclopentyl, hexyl, and cyclohexyl Wait. Among these, from the viewpoint of sensitivity, methyl, ethyl, propyl, or butyl is preferred, methyl or ethyl is more preferred, and methyl is more preferred. Examples of the substituent which the alkyl group may have include: an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a halogen atom such as F, Cl, Br, I, a hydroxyl group, a nitro group, etc., From the viewpoint of solvent solubility, a methoxy group or a hydroxyl group is preferred. From the viewpoint of sensitivity, it is preferably unsubstituted.

Examples of the aromatic ring group in R ¹ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The aromatic ring group in R ¹ may contain a condensed ring, but the number of rings contained in the condensed ring is two or less. From the viewpoint of insulation, the aromatic ring group is preferably a monocyclic ring. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. When it is more than the said lower limit value, storage stability tends to become favorable, and when it is less than the said upper limit value, insulation property tends to become favorable.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring having two or less rings. Examples of the aromatic hydrocarbon ring group include groups such as a benzene ring, a naphthalene ring, a cyclopentadiene ring, an indene ring, a fluorene ring, and a fluorene ring having one free atomic valence. The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring having two or less rings. Examples of the aromatic heterocyclic group include a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thioran ring, a pyridine ring, a 1,3-oxazole ring, Isoxazole ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furfuryl ring, pyridine ring, pyrimidine ring, data ring, 1,3,5-tricyclic ring, benzofuran ring, 2-benzofuran ring, benzothiophene ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indene Ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quine Ring, benzimidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, perylene ring, phthalic ring, 1,8-naphthyridine ring, purine ring, pyridine ring and other groups. Among these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having one free atomic valence is preferable, and a benzene ring having one free atomic valence is more preferable.

Examples of the substituent which the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I From the viewpoint of solvent solubility, a halogen atom, a hydroxyl group, a nitro group, and the like are preferably a methoxy group or a hydroxyl group. From the viewpoint of sensitivity, it is preferably unsubstituted.

Among these, from the viewpoint of hardenability, R ^{1 is} preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and even more preferably a methyl group.

(R ² ) In the above formula (1), R ² represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. The alkyl group in R ² may be linear, branched, or cyclic, and may also be formed by these bonds. From the viewpoint of solvent solubility, linear is preferred. Or branched, more preferably branched. The carbon number of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, particularly preferably 5 or more, and more preferably 10 or less, more preferably It is 8 or less, more preferably 7 or less, and even more preferably 6 or less. When it is more than the said lower limit value, there exists a tendency for solvent solubility to become favorable, and when it is less than the said upper limit value, there exists a tendency for high sensitivity. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, pentyl, isopentyl, cyclopentyl, hexyl, and cyclohexyl , Cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl and the like. Among these, from the viewpoint of solvent solubility, hexyl, isopropyl, isobutyl, isopentyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, or cyclohexylmethyl is preferred. The group is more preferably isobutyl, isopentyl, cyclopentylethyl or cyclohexylmethyl, and more preferably isopentyl. Examples of the substituent which the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I From the viewpoint of solvent solubility, halogen atoms, hydroxyl groups, and the like are preferably alkoxy groups having 1 to 3 carbon atoms. From the viewpoint of sensitivity, it is preferably unsubstituted.

Examples of the aromatic ring group in R ² include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The aromatic ring group in R ² may contain a condensed ring, but the number of rings contained in the condensed ring is two or less. From the viewpoint of insulation, the aromatic ring group is preferably a monocyclic ring. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. When it is more than the said lower limit value, there exists a tendency for a molecule to become stable, and when it is below the said upper limit value, there exists a tendency for insulation property to become favorable.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring having two or less rings. Examples of the aromatic hydrocarbon ring group include groups such as a benzene ring, a naphthalene ring, a cyclopentadiene ring, an indene ring, a fluorene ring, and a fluorene ring having one free atomic valence. The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring having two or less rings. Examples of the aromatic heterocyclic group include a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thioran ring, a pyridine ring, a 1,3-oxazole ring, Isoxazole ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furfuryl ring, pyridine ring, pyrimidine ring, data ring, 1,3,5-tricyclic ring, benzofuran ring, 2-benzofuran ring, benzothiophene ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indene Ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quine Ring, benzimidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, perylene ring, phthalic ring, 1,8-naphthyridine ring, purine ring, pyridine ring and other groups. Among these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having one free atomic valence is preferable, and a benzene ring having one free atomic valence is more preferable.

Examples of the substituent which the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I In terms of solvent solubility, halogen atoms, hydroxyl groups, nitro groups, and the like are preferably alkoxy groups or hydroxyl groups having 1 to 3 carbon atoms. From the viewpoint of sensitivity, it is preferably unsubstituted.

Among these, from the viewpoint of sensitivity, R ^{2 is} preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and even more preferably an isoamyl group. In another aspect, R ^{2 is more} preferably isopentyl or cyclopentylethyl.

(R ³ ) In the above formula (1), R ³ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. When m is an integer of 2 or more, they may be the same as each other or may be the same. different. The alkyl group in R ³ may be linear, branched, or cyclic, and may also be formed by such bonding. From the viewpoint of solvent solubility, linear is preferred. Or branched, more preferably branched. The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and further preferably 12 or less, more preferably 8 or less, and further preferably 6 or less, and particularly preferably It is 4 or less. When it is more than the said lower limit, solvent solubility will become favorable, and when it is below the said upper limit, there exists a tendency for sensitivity to become favorable. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, pentyl, isopentyl, cyclopentyl, hexyl, and cyclohexyl Wait. Among these, from the viewpoint of sensitivity, methyl, ethyl, propyl, or isopropyl is preferable, ethyl or isopropyl is more preferable, and isopropyl is more preferable. Examples of the substituent which the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I From the viewpoint of solvent solubility, halogen atoms, hydroxyl groups, and the like are preferably alkoxy groups having 1 to 10 carbon atoms. From the viewpoint of sensitivity, it is preferably unsubstituted.

Examples of the aromatic ring group in R ³ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The aromatic ring group in R ³ may contain a condensed ring, but the number of rings contained in the condensed ring is two or less. From the viewpoint of insulation, the aromatic ring group is preferably a monocyclic ring. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. When it is more than the said lower limit value, there exists a tendency for a molecule to become stable, and when it is below the said upper limit value, there exists a tendency for insulation property to become favorable.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring having two or less rings. Examples of the aromatic hydrocarbon ring group include groups such as a benzene ring, a naphthalene ring, a cyclopentadiene ring, an indene ring, a fluorene ring, and a fluorene ring having one free atomic valence. The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring having two or less rings. Examples of the aromatic heterocyclic group include a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thioran ring, a pyridine ring, a 1,3-oxazole ring, Isoxazole ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furfuryl ring, pyridine ring, pyrimidine ring, data ring, 1,3,5-tricyclic ring, benzofuran ring, 2-benzofuran ring, benzothiophene ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indene Ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quine Ring, benzimidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, perylene ring, phthalic ring, 1,8-naphthyridine ring, purine ring, pyridine ring and other groups. Among these, from the viewpoint of sensitivity, phenyl or thienyl is preferred, and phenyl is more preferred.

Examples of the substituent which the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I In terms of solvent solubility, halogen atoms, hydroxyl groups, nitro groups, and the like are preferably alkyl groups having 1 to 10 carbon atoms or alkoxy groups having 1 to 10 carbon atoms. From the viewpoint of sensitivity, it is preferably unsubstituted.

Among these, from the viewpoint of sensitivity, R ^{3 is} preferably an alkoxy group, a phenyl group, or a thienyl group having 1 to 10 carbon atoms, and more preferably a phenyl group.

(R ⁴ ) In the above formula (1), R ⁴ represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aromatic ring group which may have a substituent, a hydroxyl group, or a nitro group. Through the divalent link base bond, when n is an integer of 2 or more, they may be the same or different. In R ⁴ , the term "these bonds can be bonded via a divalent linking group" means that R ⁴ can be bonded to a benzene ring of the formula (1) via a linking group of a divalent group.

The alkyl group in R ⁴ may be linear, branched, or cyclic, and may also be formed by such bonding. From the viewpoint of solvent solubility, linear is preferred. Or branched, more preferably branched. The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and further preferably 12 or less, more preferably 8 or less, and further preferably 6 or less, and particularly preferably It is 4 or less. When it is more than the said lower limit, solvent solubility will become favorable, and when it is below the said upper limit, there exists a tendency for sensitivity to become favorable. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, pentyl, isopentyl, cyclopentyl, hexyl, and cyclohexyl Wait. Among these, from the viewpoint of sensitivity, methyl, ethyl, propyl, or isopropyl is preferable, ethyl or isopropyl is more preferable, and isopropyl is more preferable. Examples of the substituent which the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I From the viewpoint of solvent solubility, halogen atoms, hydroxyl groups, and the like are preferably alkoxy groups having 1 to 10 carbon atoms. From the viewpoint of sensitivity, it is preferably unsubstituted.

The alkoxy group in R ⁴ may be linear or branched. From the viewpoint of sensitivity, it is preferably linear. The number of carbon atoms of the alkoxy group is not particularly limited, but it is usually 1 or more, preferably 2 or more, more preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and even more preferably 4 or less. When it is more than the said lower limit, solvent solubility will become favorable, and when it is below the said upper limit, there exists a tendency for sensitivity to become favorable. Specific examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, third butoxy, and pentyl. Oxy, isopentyloxy, cyclopentyloxy, hexyloxy, isohexyloxy, cyclohexyloxy and the like. Among these, from the viewpoint of sensitivity, a methoxy group, an ethoxy group, or a propoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and an ethoxy group is more preferable. Examples of the substituent which the alkoxy group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, A halogen atom such as I, a hydroxyl group, and the like are preferably a hydroxyl group from the viewpoint of solvent solubility. From the viewpoint of sensitivity, it is preferably unsubstituted.

Examples of the aromatic ring group in R ⁴ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The aromatic ring group in R ⁴ may contain a condensed ring, but the number of rings contained in the condensed ring is two or less, and from the viewpoint of sensitivity, two are preferred. From the viewpoint of insulation, the aromatic ring group is preferably a monocyclic ring. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. When it is more than the said lower limit value, there exists a tendency for a molecule to become stable, and when it is below the said upper limit value, there exists a tendency for insulation property to become favorable.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring having two or less rings. Examples of the aromatic hydrocarbon ring group include groups such as a benzene ring, a naphthalene ring, a cyclopentadiene ring, an indene ring, a fluorene ring, and a fluorene ring having one free atomic valence. The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring having two or less rings. Examples of the aromatic heterocyclic group include a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thioran ring, a pyridine ring, a 1,3-oxazole ring, Isoxazole ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furfuryl ring, pyridine ring, pyrimidine ring, data ring, 1,3,5-tricyclic ring, benzofuran ring, 2-benzofuran ring, benzothiophene ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indene Ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quine Ring, benzimidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, perylene ring, phthalic ring, 1,8-naphthyridine ring, purine ring, pyridine ring and other groups. Among these, from the viewpoint of sensitivity, a benzene ring, a naphthalene ring, a thiophene ring, a benzofuran ring, or a benzothiophene ring having one free atomic valence is preferable, and one having a free atomic valence is more preferable. Benzofuran ring.

Examples of the substituent which the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and an aromatic group having 4 to 12 carbon atoms. From the viewpoint of solvent solubility, a halogen atom such as a group cyclic group, F, Cl, Br, I, a hydroxyl group, a nitro group, etc. are preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. base. From the viewpoint of sensitivity, it is preferably unsubstituted.

In the case of bonding via a divalent linking group, examples of the divalent linking group include: -CH ₂ -,-(CH ₂ ) _2- , -NH-, -NHCO-, -CO-, -CS -, -COO-, -O-, -S-, etc. Among these, from the viewpoint of sensitivity, -CO-, -NH-, -O- is more preferable, and -CO- is more preferable.

R ⁴ is used to adjust solubility or light absorption. From the viewpoint of sensitivity and insulation, R ^{4 is} preferably a benzene ring bonded through a divalent linking group and a divalent linking bond. Naphthalene ring bonded, thiophene ring bonded via a divalent linking group, benzofuran ring bonded via a divalent linking group, or benzo bond bonded via a divalent linking group Thiophene ring. The divalent linking group is more preferably -CO-, and more preferably a benzofuran ring formed by -CO- bonding.

(R ⁵ ) In the above formula (1), R ⁵ represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and an aromatic ring group which may have a substituent. , Halogen atom, hydroxyl group or nitro group, when p is an integer of 2 or more, they may be the same or different.

The alkyl group in R ⁵ may be linear, branched, or cyclic, and may also be formed by such bonding. From the viewpoint of solvent solubility, linear is preferred. Or branched, more preferably branched. The number of carbon atoms of the alkyl group is not particularly limited, but it is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 5 or less, even more preferably 4 or less, and particularly preferably 3 or less. When it is more than the said lower limit, solvent solubility will become favorable, and when it is below the said upper limit, there exists a tendency for sensitivity to become favorable. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, pentyl, isopentyl, cyclopentyl, hexyl, and cyclohexyl Wait. Among these, from the viewpoint of sensitivity, methyl, ethyl, propyl, or isopropyl is preferred, methyl or ethyl is more preferred, and ethyl is more preferred. Examples of the substituent which the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I From the viewpoint of solvent solubility, halogen atoms, hydroxyl groups, and the like are preferably alkoxy groups having 1 to 10 carbon atoms. From the viewpoint of sensitivity, it is preferably unsubstituted.

The alkoxy group in R ⁵ may be linear or branched. From the viewpoint of sensitivity, it is preferably linear. The number of carbon atoms of the alkoxy group is not particularly limited, but it is usually 1 or more, preferably 2 or more, more preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and even more preferably 4 or less. When it is more than the said lower limit, solvent solubility will become favorable, and when it is below the said upper limit, there exists a tendency for sensitivity to become favorable. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a second butoxy group, a third butoxy group, and a pentyl group. Oxy, isopentyloxy, cyclopentyloxy, hexyloxy, isohexyloxy, cyclohexyloxy and the like. Among these, from the viewpoint of sensitivity, a methoxy group, an ethoxy group, or a propoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and an ethoxy group is more preferable. Examples of the substituent which the alkoxy group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, A halogen atom such as I, a hydroxyl group, and the like are preferably a hydroxyl group from the viewpoint of solvent solubility. From the viewpoint of sensitivity, it is preferably unsubstituted.

The alkylthio group in R ⁵ may be linear or branched. From the viewpoint of sensitivity, it is preferably linear. The carbon number of the alkylthio group is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and even more preferably 4 or less. When it is more than the said lower limit, solvent solubility will become favorable, and when it is below the said upper limit, there exists a tendency for sensitivity to become favorable. Specific examples of the alkylthio group include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, third butylthio, pentylthio, and isopentylthio. Base, cyclopentylthio, hexylthio, isohexylthio, cyclohexylthio, and the like. Among these, from the viewpoint of sensitivity, a methylthio group, an ethylthio group, or a propylthio group is preferable, a methylthio group or an ethylthio group is more preferable, and an ethylthio group is more preferable. Examples of the substituent which the alkylthio group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, A halogen atom such as I, a hydroxyl group, and the like are preferably a hydroxyl group from the viewpoint of solvent solubility. From the viewpoint of sensitivity, it is preferably unsubstituted.

Examples of the aromatic ring group in R ⁵ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The aromatic ring group in R ⁵ may contain a condensed ring, but the number of rings contained in the condensed ring is two or less. From the viewpoint of insulation, the aromatic ring group is preferably a monocyclic ring. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. When it is more than the said lower limit value, there exists a tendency for a molecule to become stable, and when it is below the said upper limit value, there exists a tendency for insulation property to become favorable.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring having two or less rings. Examples of the aromatic hydrocarbon ring group include groups such as a benzene ring, a naphthalene ring, a cyclopentadiene ring, an indene ring, a fluorene ring, and a fluorene ring having one free atomic valence. The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring having two or less rings. Examples of the aromatic heterocyclic group include a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thioran ring, a pyridine ring, a 1,3-oxazole ring, Isoxazole ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furfuryl ring, pyridine ring, pyrimidine ring, data ring, 1,3,5-tricyclic ring, benzofuran ring, 2-benzofuran ring, benzothiophene ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indene Ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quine Ring, benzimidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, perylene ring, phthalic ring, 1,8-naphthyridine ring, purine ring, pyridine ring and other groups. Among these, from the viewpoint of sensitivity, phenyl or thienyl is preferred, and phenyl is more preferred.

Examples of the substituent which the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I In terms of solvent solubility, halogen atoms, hydroxyl groups, nitro groups, and the like are preferably alkyl groups having 1 to 10 carbon atoms or alkoxy groups having 1 to 10 carbon atoms. From the viewpoint of sensitivity, it is preferably unsubstituted.

Examples of the halogen atom in R ⁵ include F, Cl, Br, and I.

Among these, from the viewpoint of sensitivity, R ^{5 is} preferably methyl, methoxy, phenyl, or thienyl, and more preferably methoxy.

(A) In the formula (1), A represents an oxygen atom or a sulfur atom. From the viewpoint of sensitivity, A is preferably an oxygen atom.

(m) In the formula (1), m represents an integer of 0 to 4. From the viewpoint of sensitivity, m is preferably 3 or less, more preferably 2 or less, even more preferably 1 or less, and even more preferably 0.

(n) In the formula (1), n represents an integer of 0 to 4. From the viewpoint of sensitivity, n is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, still more preferably 1 or less, and even more preferably 0.

(p) In the formula (1), p represents an integer of 0 to 4. From the viewpoint of sensitivity, p is preferably 3 or less, more preferably 2 or less, even more preferably 1 or less, and even more preferably 0.

Specific examples of the photopolymerization initiator (c1) include the following.

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7]

In the above formula, C ₃ H ₇ represents isopropyl.

<Other photopolymerization initiators (c2)> The photopolymerization initiator (c) in the present invention is for the purpose of adjusting properties such as sensitivity and internal hardening properties of the photosensitive resin composition, in addition to the photopolymerization initiator (c1) ) May contain other photopolymerization initiators (c2). Examples of other photopolymerization initiators (c2) include metallocene compounds containing titanocene compounds described in Japanese Patent Laid-Open No. 59-152396 and Japanese Patent Laid-Open No. 61-151197; Hexaryl biimidazole derivatives described in Japanese Patent Laid-Open No. 2000-56118; halomethylated oxadiazole derivatives and halomethyl trimerates described in Japanese Patent Laid-Open No. 10-39503 Free radicals such as species, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters Active agents, α-aminoalkyl phenone derivatives; oxime ester derivatives described in Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2006-36750, and the like.

Specifically, for example, examples of the metallocene compound include dicyclopentadienyl titanium dichloride, dicyclopentadienyl biphenyl titanium, and dicyclopentadienyl bis (2,3,4, 5,6-pentafluorophenyl) titanium, dicyclopentadienyl bis (2,3,5,6-tetrafluorophenyl) titanium, dicyclopentadienyl bis (2,4,6-trifluoro Phenyl) titanium, dicyclopentadienyl bis (2,6-difluorophenyl) titanium, dicyclopentadienyl bis (2,4-difluorophenyl) titanium, bis (methylcyclopentadiene) Alkenyl) bis (2,3,4,5,6-pentafluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2,6-difluorophenyl) titanium, dicyclopentadiene [2,6-difluoro-3- (pyrrolyl) -phenyl] titanium and the like.

Examples of the biimidazole derivatives include 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (2'-chlorophenyl) -4,5- Bis (3'-methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) ) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5-diphenylimidazole dimer, and the like.

Examples of the halomethylated fluorenediazole derivatives include 2-trichloromethyl-5- (2'-benzofuranyl) -1,3,4-fluorenediazole and 2-trichloro Methyl-5- [β- (2'-benzofuranyl) vinyl] -1,3,4-fluorenediazole, 2-trichloromethyl-5- [β- (2 '-(6' '-Benzofuryl) vinyl)]-1,3,4-fluorenediazole, 2-trichloromethyl-5-furanyl-1,3,4-fluorenediazole, and the like.

Examples of the halomethyl mesitane derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) mesa, and 2- (4-methoxynaphthalene). Methyl) -4,6-bis (trichloromethyl) tris, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) tris, 2- (4-ethoxy Carbonylcarbonylnaphthyl) -4,6-bis (trichloromethyl) are all equal.

Examples of the α-aminoalkyl phenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-olinylpropan-1-one, and 2-benzyl 2-dimethylamino-1- (4-olinylphenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-olinylphenyl) butan-1- Ketone, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminophenylacetone, 2-ethylbenzoate Hexyl-1,4-dimethylamine ester, 2,5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzyl Fluorenyl) coumarin, 4- (diethylamino) chalcone and the like.

As other photopolymerization initiators, especially in terms of sensitivity, oxime ester derivatives are effective, and sometimes it may be disadvantageous in terms of sensitivity due to the inclusion of colorants. Therefore, such oxime ester derivatives are particularly excellent in sensitivity. The oxime ester compound (1) represented by the following general formula (c2-1) or the oxime ester compound (2) represented by the following general formula (c2-2) is useful. Among the oxime ester derivatives, the oxime ester compound (1) is particularly preferred from the viewpoint of sensitivity and adhesion to the substrate. The oxime ester derivatives have both a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates free radicals. Therefore, a small amount can make the sensitivity higher, and it can stabilize the thermal response. A small amount can be designed as a high sensitivity. A photosensitive resin composition. In particular, from the viewpoint of light absorption of the I-ray (365 nm) of the exposure light source, the oxime ester-based compound containing a substituted carbazole group (a group having a substituted carbazole ring) ( In the case of 1), the structural characteristics are well expressed and better. At present, in the market, BM (black matrix) with high shading degree and thin film is required, and the pigment concentration is gradually increasing, which is especially effective in this situation.

[Chemical 8]

[Chemical 9]

In the formulae (c2-1) and (c2-2), R ^a to R ^c each independently represent an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.

As commercially available products of such oxime ester compounds (1), there are OXE-02 manufactured by BASF Corporation, TR-PBG-304 or TR-PBG-314 manufactured by Changzhou Qiangli Electronics Co., Ltd., and the like.

Specific examples of the preferred oxime ester compounds include the compounds exemplified below, but they are not limited in any way.

[Chemical 10]

[Chemical 11]

[Chemical 12]

Other examples include: benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; 2-methylanthraquinone, 2-ethylanthraquinone, and 2-tert-butylanthracene Anthraquinone derivatives such as quinone and 1-chloroanthraquinone; benzophenone, Michelin, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone , Benzophenone derivatives such as 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenone, α-hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl Ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4'-methylthiophenyl) -2-olinyl-1-acetone, 1,1,1 -Acetophenone derivatives such as trichloromethyl- (p-butylphenyl) ketone; 9-oxysulfur , 2-ethylthioketone, 2-isopropylthioketone, 2-chloro-9-oxosulfan 9-oxothione, 2,4-dimethylthioketone, 2,4-diethylthioketone, 2,4-diisopropylthioketone, etc. Derivatives; benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (p-methoxyphenyl) acyl Acridine derivatives such as pyridine; morphine derivatives such as 9,10-dimethylbenzophenone; anthrone derivatives such as benzoxanthone.

<Sensitizing pigment> In the photopolymerization initiator, if necessary, in order to increase the sensitivity of the sensitivity, a sensitizing pigment corresponding to the wavelength of the light source of the image exposure can be used together. Examples of such sensitizing dyes include dibenzopyran pigments described in Japanese Patent Laid-Open No. 4-221958, Japanese Patent Laid-Open No. 4-219756, Japanese Patent Laid-Open No. 3-239703, and Japan Coumarin pigments with heterocyclic rings described in Japanese Patent Laid-Open No. 5-289335, 3-ketocoumarin compounds described in Japanese Patent Laid-Open No. 3-239703, and Japanese Patent Laid-Open No. 5-289335. 2. Pyrromethene pigments described in Japanese Patent Laid-Open No. 6-19240; others, Japanese Patent Laid-Open No. 47-2528, Japanese Patent Laid-Open No. 54-155292, and Japanese Patent Laid-Open No. 45-37377 Gazette, Japanese Patent Laid-Open Publication No. 48-84183, Japanese Patent Laid-Open Publication No. 52-112681, Japanese Patent Laid-Open Publication No. 58-15503, Japanese Patent Laid-Open Publication No. 60-88005, Japanese Patent Laid-Open Publication Sho 59-56403, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 57-168088, Japanese Patent Laid-Open No. 5-107761, Japanese Patent Laid-Open No. 5-210240, Japanese Patent JP 4-288818 The described dye having a skeleton of benzene, dialkylamino and the like.

Among these sensitizing dyes, amine-containing sensitizing dyes are preferable, and compounds having an amine group and a phenyl group in the molecule are more preferable. In particular, preferred are, for example: 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminodiphenyl Benzophenone-based compounds such as methanone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone; 2- (P-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5] benzo Oxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diamino Ethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethyl Aminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) ) Pyrimidine-containing compounds such as p-dialkylaminophenyl and the like. Among them, 4,4'-dialkylaminobenzophenone is most preferred. The sensitizing dye may be used alone or in combination of two or more.

(c) The content ratio of the photopolymerization initiator is not particularly limited, and it is usually 1% by mass or more, preferably 2% by mass or more, and more preferably 2% by mass of the total solid content of the photosensitive resin composition of the present invention. 3 mass or more, usually 30 mass% or less, preferably 20 mass% or less, more preferably 15 mass% or less, still more preferably 10 mass% or less, still more preferably 8 mass% or less, and even more preferably 5 mass %the following. When it is more than the said lower limit value, there exists a tendency which can suppress the fall of sensitivity, and when it is below the said upper limit value, there exists a tendency for the solubility of the unexposed part to the developing solution to become favorable. The combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, even more preferably 2 to 15% by mass, still more preferably 3 to 10% by mass, and even more preferably 3 -8 mass%, and more preferably 3 to 5 mass%.

The content ratio of the photopolymerization initiator (c1) is not particularly limited, and it is usually 0.3% by mass or more, preferably 0.5% by mass or more, of all the solid components of the photosensitive resin composition of the present invention. It is preferably 1% by mass or more, further preferably 2% by mass or more, even more preferably 3% by mass or more, usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably It is 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less. When it is more than the said lower limit value, there exists a tendency for sensitivity and insulation to be compatible easily, and when it is less than the said upper limit value, there exists a tendency for the solubility of the unexposed part to the developing solution to become favorable. The combination of the upper limit and the lower limit is preferably 0.3 to 30% by mass, more preferably 0.3 to 20% by mass, still more preferably 0.5 to 15% by mass, even more preferably 1 to 10% by mass, and even more preferably 2 -8 mass%, and more preferably 3 to 5 mass%. The content ratio of the photopolymerization initiator (c1) to the total amount of the (c) photopolymerization initiator is not particularly limited, but it is usually 30% by mass or more, preferably 50% by mass or more, and more preferably 70% by mass The above is more preferably 80% by mass or more, still more preferably 90% by mass or more, even more preferably 95% by mass or more, and usually 100% by mass or less. Moreover, when it is more than the said lower limit value, there exists a tendency for insulation property to become high. In addition, the resistivity can also be adjusted by the content ratio of the photopolymerization initiator (c1) to the total amount of the (c) photopolymerization initiator.

In the case of using a sensitizing dye, the content ratio is not particularly limited, and it is usually 0 to 20% by mass, preferably 0 to 15% by mass, in all the solid components of the photosensitive resin composition. Further, It is preferably 0 to 10% by mass.

<(A) Alkali soluble resin> The photosensitive resin composition of this invention contains (a) alkali soluble resin. (a) The alkali-soluble resin is not particularly limited as long as it changes the solubility of the exposed portion and the non-exposed portion in the development of alkali after exposing the coating film obtained by applying and drying the photosensitive resin composition. Is preferably an alkali-soluble resin having a carboxyl group. Moreover, those having an ethylenically unsaturated group are preferred, and alkali-soluble resins having an ethylenically unsaturated group and a carboxyl group are more preferred. Specific examples include epoxy (meth) acrylate resins or acrylic copolymer resins having a carboxyl group. Preferred ones, and more specifically, the following (A1-1), (A1-2), (A2) For -1), (A2-2), (A2-3), and (A2-4), one type may be used, or two or more types may be used. Among the above, epoxy (meth) acrylate resins having a carboxyl group are preferred, and (A1-1) and (A1-2) are particularly preferred.

An epoxy (meth) acrylate resin having a carboxyl group reacts an epoxy resin with an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid having a carboxyl group to form a reactant, and further A resin obtained by reacting a polybasic acid and / or its anhydride with a hydroxyl group formed in a reaction between reactants. Before reacting a polybasic acid and / or its anhydride with a hydroxyl group, a resin obtained by reacting a polybasic acid and / or its anhydride after reacting a compound having two or more substituents that can react with the hydroxyl group is also included in the ring. Oxygen (meth) acrylate resin. Further, a resin obtained by reacting a compound having a further reactive functional group with a carboxyl group of the resin obtained in the above reaction is also included in the epoxy (meth) acrylate resin. Thus, the epoxy (meth) acrylate resin does not substantially have an epoxy group in the chemical structure, and is not limited to "(meth) acrylate", but epoxy resin is the raw material and "(meth) acrylate" As a representative example, so named according to custom.

When producing a color filter, generally, an unexposed portion is dissolved in an alkaline developing solution. As the alkali-soluble resin, a polymer resin having acidic functional groups such as a hydroxyl group, a carboxyl group, a phosphate group, and a sulfonic acid group can be suitably used. Among these, a polymer resin having a carboxyl group is preferred from the viewpoint of solubility in an alkaline developer. In addition, although the acidity of the phosphate group or sulfonic acid group is higher than that of the carboxyl group, it easily reacts with the initiator, monomer, dispersant, and other additives having a basic group in the photosensitive resin composition. Poor situation.

Examples of the epoxy (meth) acrylate resin having a carboxyl group include the following epoxy (meth) acrylate resin (A1-1) and / or epoxy (meth) acrylate resin (A1-2 ).

<Epoxy (meth) acrylate resin (A1-1)> By adding an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group, An alkali-soluble resin obtained by reacting a polybasic acid and / or its anhydride. <Epoxy (meth) acrylate resin (A1-2)> By adding an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, An alkali-soluble resin obtained by reacting a polyhydric alcohol and a polybasic acid and / or an anhydride thereof.

<Epoxy (meth) acrylate resin (A1-1)> As the epoxy resin used as a raw material, for example, bisphenol A type epoxy resin (for example, "jER (registered trademark) manufactured by Mitsubishi Chemical Corporation" can be preferably used. ; The same below) 828 "," jER1001 "," jER1002 "," jER1004 "," NER-1302 "(epoxy equivalent 323, softening point 76 ° C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F-type resin ( For example, "jER807", "jER4004P", "jER4005P", "jER4007P" manufactured by Mitsubishi Chemical Corporation, "NER-7406" (epoxy equivalent 350, softening point 66 ° C) manufactured by Nippon Kayaku Co., Ltd., bisphenol S Type epoxy resin, biphenyl glycidyl ether (such as "jERYX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (such as "EPPN (registered trademark; the same below) made by Nippon Kayaku Co., Ltd. -201 "," JER-152 "," jER-154 "manufactured by Mitsubishi Chemical Corporation," DEN-438 "manufactured by Dow Chemical Co., Ltd., (ortho, meta, p) cresol novolac type epoxy resin (e.g. Japanese "EOCN (registered trademark; the same below) -102S", "EOCN-1020" manufactured by pharmaceutical companies , "EOCN-104S"), triglycidyl isocyanurate (e.g., "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.), triphenol methane type epoxy resin (e.g., "EPPN-501" manufactured by Nippon Kayaku Co., Ltd. "," EPPN-502 "," EPPN-503 "), alicyclic epoxy resin (" Celloxide (registered trademark; the same below) 2021P "," Celloxide EHPE "manufactured by Daicel), A glycidylated epoxy resin (e.g., "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), and the following general formula ( a1) to (a5). Specifically, as the epoxy resin represented by the following general formula (a1), "XD-1000" manufactured by Nippon Kayaku Co., Ltd., and as the epoxy resin represented by the following general formula (a2), As the "NC-3000" manufactured by Nippon Kayaku Co., Ltd., as the epoxy resin represented by the following general formula (a4), "ESF-300" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. can be cited.

[Chemical 13]

In the general formula (a1), b11 is an average value and represents a number from 0 to 10. R ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. In addition, a plurality of R ^{11 in} one molecule may be the same as or different from each other.

[Chemical 14]

In said general formula (a2), b12 is an average value, and shows the number of 0-10. R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, phenyl, naphthyl, or biphenyl. Furthermore, a plurality of R ²¹ present in one molecule may be the same as or different from each other.

[Chemical 15]

In the general formula (a3), X represents a linking group represented by the following general formula (a3-1) or (a3-2). Among them, the molecular structure includes one or more adamantane structures. b13 represents an integer of 2 or 3.

[Chemical 16]

In the general formulae (a3-1) and (a3-2), R ³¹ to R ³⁴ and R ³⁵ to R ³⁷ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, and a carbon number which may have a substituent of 1. The alkyl group of -12 or phenyl which may have a substituent. In addition, * in the formula represents a bonding site in the general formula (a3).

[Chemical 17]

In the general formula (a4), p and q each independently represent an integer of 0 to 4. R ⁴¹ and R ⁴² each independently represent an alkyl group or a halogen atom having 1 to 20 carbon atoms. R ⁴³ and R ⁴⁴ each independently represent an alkylene group having 1 to 5 carbon atoms. x and y each independently represent an integer of 0 or more.

[Chemical 18]

In the general formula (a5), R ⁵¹ to R ⁵⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R ⁵⁵ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R ⁵⁶ each independently represents an alkylene group having 1 to 5 carbon atoms. k represents an integer of 1 to 5, l represents an integer of 0 to 13, and m each independently represents an integer of 0 to 5. Among these, it is preferable to use an epoxy resin represented by any one of the general formulae (a1) to (a5).

Examples of the α, β-unsaturated monocarboxylic acid and / or the α, β-unsaturated monocarboxylic acid having a carboxyl group include (meth) acrylic acid, butenoic acid, o-, m-, p-vinylbenzoic acid, (Meth) acrylic acids such as α-haloalkyl, alkoxy, halogen, nitro, cyano substituted monocarboxylic acids, 2- (meth) acryloxyethyl succinic acid, 2- (methyl ) Acrylic ethoxyethyl adipate, 2- (meth) acrylic ethoxyethyl phthalic acid, 2- (meth) acrylic ethoxyethyl hexahydrophthalic acid, 2- ( (Meth) acryloxyethylmaleic acid, 2- (meth) acryloxypropylsuccinic acid, 2- (meth) acryloxypropyl adipic acid, 2- (formaldehyde) Propyl) propenyloxypropyltetrahydrophthalic acid, 2- (meth) propenyloxypropylphthalic acid, 2- (meth) propenyloxypropylmaleic acid, 2- (meth) acryloxybutyl succinic acid, 2- (meth) acryloxybutyl adipic acid, 2- (meth) acryloxybutyl hydrophthalic acid, 2 -(Meth) acryloxybutyl phthalic acid, 2- (meth) acryloxybutyl maleic acid as (meth) acrylates Examples include monomers having lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone added to (meth) acrylic acid and having one hydroxyl group at the terminal, Or, for example, a hydroxyalkyl (meth) acrylate having 1 hydroxy monomer at the terminal, or a compound such as pentaerythritol tri (meth) acrylate having 1 hydroxy at the terminal, succinic acid (anhydride), Phthalic acid (anhydride), maleic acid (anhydride), and other acids (anhydrides), (meth) acrylates having one or more ethylenically unsaturated groups and one carboxyl group at the terminal. Moreover, a (meth) acrylic acid dimer etc. are also mentioned.

Among these, (meth) acrylic acid is particularly preferable in terms of sensitivity. As a method for adding an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known method can be used. For example, an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group and an epoxy resin can be used at a temperature of 50 to 150 ° C in the presence of an esterification catalyst. Perform the reaction. As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, benzyldiethylamine, tetramethylammonium chloride, tetraethylammonium chloride, Quaternary ammonium salts such as dodecyltrimethylammonium chloride.

Furthermore, the epoxy resin, the α, β-unsaturated monocarboxylic acid, the α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used singly or in combination of two or more. The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of epoxy resin, and more preferably The range is 0.7 to 1.1 equivalents. By setting the amount of the α, β-unsaturated monocarboxylic acid and / or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the above lower limit value or more, the introduction amount of the unsaturated group becomes sufficient, and then The reaction with the polybasic acid and / or its anhydride becomes sufficient, and the tendency of a large number of epoxy groups to remain can be suppressed. On the other hand, by using the above-mentioned amount below the above-mentioned upper limit value, the presence of α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group can be prevented from remaining as unreacted substances. The tendency.

Examples of the polybasic acid and / or its anhydride include those selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, Trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorobridged acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid One or two or more of acids and anhydrides thereof.

Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid. Or such anhydrides. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride or biphenyltetracarboxylic dianhydride.

Regarding the addition reaction of a polybasic acid and / or its anhydride, a known method can also be used. It can be used for α, β-unsaturated monocarboxylic acids and / or α, β-unsaturated carboxyl groups on epoxy resins. Under the same conditions for the addition reaction of the monocarboxylic acid ester, the reaction is continued to obtain the target substance. The addition amount of the polybasic acid and / or its anhydride component is preferably such that the acid value of the carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mgKOH / g, and more preferably 20 To the extent of ~ 140 mgKOH / g. When it is more than the said lower limit, there exists a tendency for alkaline developability to become favorable, and when it is less than the said upper limit, there exists a tendency for hardenability to become favorable.

<Epoxy (meth) acrylate resin (A1-2)> During the addition reaction of the polybasic acid and / or its anhydride of the resin (A1-1), trimethylolpropane, pentaerythritol, and dipentaerythritol may be added. An epoxy (meth) acrylate resin (A1-2) is obtained by introducing a multi-branched structure such as a polyhydric alcohol. Epoxy (meth) acrylate resins (A1-1) and (A1-2) are usually produced by the combination of epoxy resin with α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated mono After the polybasic acid and / or its anhydride are mixed in the carboxylic acid ester reactant, or the epoxy resin is reacted with the α, β-unsaturated monocarboxylic acid and / or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group A polybasic acid and / or an anhydride thereof and a polyhydric alcohol are mixed with the mixture, and then heated to obtain the polybasic acid. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyol is not particularly limited. By heating, a mixture of a polybasic acid and / or its anhydride with an epoxy resin and an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group and a mixture of polyols Any hydroxyl group present in the reaction proceeds.

The epoxy (meth) acrylate resin having a carboxyl group may be used alone or as a mixture of two or more resins. As for the amount of the polyol used, from the viewpoint of suppressing thickening or gelation and exhibiting effects, it is relative to an epoxy resin, an α, β-unsaturated monocarboxylic acid, and / or an α, β-unsaturation having a carboxyl group. The reaction product of the monocarboxylic acid ester is usually about 0.01 to 0.5 mass times, preferably about 0.02 to 0.2 mass times.

The acid value of the epoxy (meth) acrylate resin having a carboxyl group is generally 10 mgKOH / g or more, preferably 50 mgKOH / g or more, more preferably 80 mgKOH / g or more, and preferably 200 mgKOH / g or less , More preferably below 150 mgKOH / g. When it is more than the said lower limit value, there exists a tendency for developability to become favorable, and when it is less than the said upper limit value, there exists a tendency for alkali resistance to become favorable. The combination of the upper limit and the lower limit is preferably 10 to 200 mgKOH / g, more preferably 50 to 150 mgKOH / g, and even more preferably 80 to 150 mgKOH / g.

The weight average molecular weight (Mw) in terms of polystyrene conversion of the epoxy (meth) acrylate resin having a carboxyl group measured by gel permeation chromatography (GPC) is preferably 1,000 or more, more preferably 1,500 or more, and further It is preferably 2,000 or more, and particularly preferably 5,000 or more. In addition, it is preferably 20,000 or less, more preferably 15,000 or less, even more preferably 10,000 or less, even more preferably 8000 or less, and even more preferably 6,000 or less. When it is more than the said lower limit, there exists a tendency for sensitivity, coating-film strength, and alkali resistance to become favorable, and when it is below the said upper limit, there exists a tendency for the developability or re-solubility to become favorable. As a combination of the upper limit and the lower limit, it is preferably 1,000 to 20,000, more preferably 1500 to 20,000, still more preferably 1500 to 15,000, still more preferably 2,000 to 15,000, even more preferably 2000 to 10,000, and even more preferably 2000. ~ 8000, particularly preferably 2000 ~ 6000.

<Acrylic copolymer resin (A2-1) (A2-2) (A2-3) (A2-4)> As the acrylic copolymer resin, for example, Japanese Patent Laid-Open No. 7-207211 and Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-140144, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 2000-56118, Japanese Patent Laid-Open No. Various polymer compounds described in various publications, such as 2003-233179 and Japanese Patent Laid-Open No. 2007-270147, preferably include the following resins (A2-1) to (A2-4). Among them, particularly The resin is preferably (A2-1).

(A2-1): For a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, at least a part of the epoxy group in the copolymer is added to an unsaturated monobasic acid The resulting resin, or a resin obtained by adding at least a part of the hydroxyl groups generated by the addition reaction to a polybasic acid anhydride (A2-2): a linear alkali-soluble resin (A2-3) containing a carboxyl group in the main chain : A resin obtained by adding a carboxyl portion of the above (A2-2) resin to an unsaturated compound containing an epoxy group (A2-4): (meth) acrylic resin

From the viewpoint of sensitivity, the photosensitive resin composition of the present invention further preferably contains at least any one of (A1-1), (A1-2), (A2-1), and (A2-3) as the content. Alkali soluble resin with ethylenically unsaturated groups. From the viewpoint of surface hardenability, the photosensitive resin composition of the present invention preferably contains at least one of (A1-1) and (A1-2) as an epoxy (meth) acrylate resin. Alkali soluble resin with ethylenically unsaturated groups.

The photosensitive resin composition of the present invention may be used in combination with other alkali-soluble resins. Other alkali-soluble resins are not limited, and can be selected from resins generally used in photosensitive resin compositions for color filters. Examples include alkali-soluble resins described in Japanese Patent Laid-Open No. 2007-271727, Japanese Patent Laid-Open No. 2007-316620, and Japanese Patent Laid-Open No. 2007-334290.

(a) The content ratio of the alkali-soluble resin in the total solid content of the photosensitive resin composition of the present invention is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, and even more preferably 20% by mass or less. By setting it above the lower limit value, the solubility of the unexposed portion in the developing solution tends to be good, and by setting it below the upper limit value, it is possible to suppress excessive penetration of the developing solution into the exposed portion, The sharpness or adhesion of the image tends to be good. The combination of the upper limit and the lower limit is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, even more preferably 10 to 50% by mass, even more preferably 15 to 30% by mass, and even more preferably 15 -20% by mass. As described above, the photosensitive resin composition of the present invention preferably contains the above-mentioned (A1-1), (A1-2), (A2-1), (A2-2), (A2-3), and When at least one of (A2-4) is (a) an alkali-soluble resin, when it contains other alkali-soluble resins, its content ratio is 20% by mass or less with respect to the total of the alkali-soluble resin (a), and preferably 10% by mass %the following.

<(B) Photopolymerizable monomer> The photosensitive resin composition of the present invention contains (b) a photopolymerizable monomer in terms of sensitivity and the like. Examples of the (b) photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter sometimes referred to as "ethylenic monomer"). Specific examples include (meth) acrylic acid, (meth) acrylic acid alkyl esters, acrylonitrile, styrene, and monoesters of a carboxylic acid and a polyhydric or monohydric alcohol having one ethylenically unsaturated bond, and the like. .

In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is usually 2 or more, preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, and even more preferably 6 or more. It is usually 10 or less, preferably 8 or less. When it is more than the said lower limit value, there exists a tendency for a photosensitive resin composition to become high sensitivity, and when it is below the said upper limit value, there exists a tendency for the hardening shrinkage at the time of a polymerization to become small. The combination of the upper limit and the lower limit is preferably 2 to 10, more preferably 3 to 10, still more preferably 4 to 8, still more preferably 5 to 8, and even more preferably 6 to 8. Examples of the polyfunctional ethylenic monomer include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; and an aliphatic polyhydroxy compound and an aromatic An ester obtained by an esterification reaction of a polyhydroxy compound such as a polyhydroxy compound with an unsaturated carboxylic acid and a polycarboxylic acid.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. Acrylates of aliphatic polyhydroxy compounds such as esters, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, The acrylates of the exemplified compounds are replaced with the methacrylates of the methacrylate, the same is replaced by the iconate of the iconate, the butenoate of the butenoate, or the maleate Esters of maleic acid and the like.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, and resorcinol dimethyl. Acrylates, catechol triacrylates and other aromatic polyhydroxy compounds such as acrylates and methacrylates. The ester obtained by the esterification reaction of a polycarboxylic acid, an unsaturated carboxylic acid, and a polyhydroxy compound is not necessarily a single substance, and representative specific examples include acrylic acid, phthalic acid, and ethylene glycol. Condensates of acrylic acid, condensates of maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid, and pentaerythritol, and condensates of acrylic acid, adipic acid, butanediol, and glycerol.

In addition, as examples of the polyfunctional ethylenic monomer used in the present invention, it is useful to use a polyisocyanate compound and a hydroxyl-containing (meth) acrylate, or a polyisocyanate compound and a polyol and a hydroxyl-containing (methyl (Meth) acrylic acid urethanes obtained by the reaction of methacrylic acid esters; epoxy acrylates such as polyhydric epoxy compounds and (meth) acrylic acid hydroxyl esters or (meth) acrylic acid addition reactants ; Acrylamines such as ethacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate. These can be used alone or in combination of two or more.

(b) The content ratio of the photopolymerizable monomer in the total solid content of the photosensitive resin composition is usually 1% by mass or more, preferably 5% by mass or more, and usually 90% by mass or less, preferably It is 70% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass or less, and even more preferably 10% by mass or less. When the content ratio of the photopolymerizable monomer is equal to or more than the above-mentioned lower limit value, there is a tendency that the light hardening by ultraviolet irradiation is improved and the alkali developability is also good. By making it below the said upper limit, there exists a tendency for the permeability of a developing solution to an exposure part to become moderate, and a favorable image can be obtained. The combination of the upper limit and the lower limit is preferably 1 to 90% by mass, more preferably 1 to 70% by mass, even more preferably 1 to 50% by mass, even more preferably 1 to 30% by mass, and even more preferably 5 It is -20% by mass, and more preferably 5-10% by mass.

<(D) Colorant> The photosensitive resin composition of the present invention contains (d) a colorant. By containing (d) a coloring material, formation of a coloring pattern, such as a black matrix and a coloring spacer, etc. can be achieved. The colorant refers to a person who colored the photosensitive resin composition of the present invention.

The colorant (d) contained in the photosensitive resin composition of the present invention contains high-resistance carbon black (d1). The high-resistance carbon black (d1) is not particularly limited as long as the carbon black is subjected to a high-resistance treatment. Examples of the high-resistance treatment include a surface coating treatment by a resin (Japanese Patent Laid-Open No. 2002-249678 and a Japanese Patent Publication No. 2016-65992), and a surface coating treatment by a dye (International Publication No. 2013/129555), surface oxidation treatment (Japanese Patent No. 4464081), or surface modification treatment with organic groups having an ionic group (Japanese Patent Publication No. 2008-517330).

More specifically, in the surface coating method by resin described in Japanese Patent Laid-Open No. 2002-249678, carbon black is subjected to a graft reaction treatment so that a functional group is bonded to the surface of the carbon black, and then, The resin is treated to cover the surface of the carbon black with a resin. Here, the compound used in the graft reaction treatment of carbon black is a compound capable of reacting with a polymerization-inhibiting functional group, and examples thereof include photopolymerizable compounds having an ethylenically unsaturated double bond and other functional groups. . Examples of the functional group other than the ethylenically unsaturated double bond include an epoxy group, a thioepoxy group, an aziridinyl group, an oxazoline group, an N-hydroxyalkylamidoamino group, an isocyanate group, Specific examples of the photopolymerizable compound include glycidyl (meth) acrylate, allyl glycidyl ether, 2,3-epithiopropyl (meth) acrylate, and N- ( (Meth) acrylfluorenylaziridine, 2- (1-aziridinyl) ethyl (meth) acrylate, 2-isopropenyl-2-oxazoline, N-hydroxyethyl (meth) propylene Amidine, ethyl isocyanate (meth) acrylate, allylamine, and the like. The carbon black-coated resin is preferably an epoxy resin, and particularly preferably a polyfunctional epoxy resin. Specific examples of the polyfunctional epoxy resin include a glycidylamine-based epoxy resin, a triphenylglycidylmethane-based epoxy resin, a tetraphenylglycidylmethane-based epoxy resin, and an aminophenol type ring. Oxygen resin, diaminodiphenylmethane type epoxy resin, phenol novolac type epoxy resin, o-cresol type epoxy resin, bisphenol A novolac type epoxy resin, etc.

In the method of surface coating by dyes described in International Publication No. 2013/129555, first, carbon black and water are mixed to form a slurry, the carbon black is heated and stirred for a specific time, the carbon black is washed, and then washed again after cooling. . Next, water is added to the obtained carbon black to make a slurry again, an oxidizing agent is added, and the mixture is stirred at a specific temperature for a specific time, and the surface of the carbon black is subjected to an oxidation treatment and washed with water. The oxidation treatment may be performed a plurality of times by changing the type of the oxidizing agent as necessary. Next, the obtained oxidized carbon black is mixed with water to make a slurry again, and a dye is added so that the target dye-coated carbon black becomes the above-mentioned specific content, and the mixture is stirred at 40 to 90 ° C. for 1 to 5 hours to make The dye is adsorbed and coated on the surface of carbon black. Furthermore, mols of metals or metal salts such as dyes are added and stirred at 30 to 70 ° C. for 1 to 5 hours. The dyes are laked with the metal or metal salts to fix the dyes to the surface of carbon black. In addition, after cooling, washing with water, filtering, and drying, the target dye-coated carbon black can be obtained. The dye used in the dye-coated carbon black is not particularly limited as long as it can be adsorbed on the surface of carbon black. Known basic dyes, acid dyes, direct dyes, reactive dyes, etc. The carboxyl group interacts with functional groups on carbon black, the amine group reacts with an alkali-soluble resin, and can dissolve aluminum sulfate and other aspects. It can make better use of anionic or nonionic dyes. In order to increase the light-shielding property of the obtained black matrix, it is preferable to use a dark-colored dye which is close to black and has high light absorption. Specific examples of such dyes include food color dyes such as Food Black No.1, Food Black No.2, Food Red No.40, Food Blue No.1, Food Yellow No.7, Bernacid Red 2BMN, and Basacid. (Registered trademark) Black X34 (BASF X-34) (manufactured by BASF), Kayanol (registered trademark) Red 3BL (manufactured by Nippon Kayaku Company), Dermacarbon 2GT (manufactured by Sandoz), Telon (registered trademark) Fast Yellow 4GL-175 , BASF Basacid Black SE 0228, Basacid Black X34 (BASF X-34) (made by BASF), Basacid Blue 750 (made by BASF), Bernacid Red (Bemcolors, Poughkeepsie, made by NY), BASF Basacid Black SE 0228 (BASF (Manufactured by the company) and various acid dyes, Pontamine (registered trademark) Brilliant Bond Blue A and other Pontamine Brilliant Bond Blue A and other Pontamine dyes (Bayer Chemicals Corporation, Pittsburgh, PA company), Cartasol (registered trademark) Yellow GTF Presscake (manufactured by Sandoz, Inc.); Cartasol Yellow, GTF Liquid Special 110 (manufactured by Sandoz, Inc.); Yellow Shade 16948 (manufactured by Tricon), Direct Brilliant P ink B (made by Crompton & Knowles), Carta (registered trademark) Black 2GT (made by Sandoz, Inc.), Sirius (registered trademark) Supra Yellow GD 167, Cartasol Brilliant Yellow 4GF (made by Sandoz); Pergasol (registered trademark) Yellow CGP (manufactured by Ciba-Geigy), Pyrazol Black BG (manufactured by JCI), Diazol Black RN Quad (manufactured by JCJ), Pontamine Brilliant Bond Blue; direct dyes of various colors such as Berncolor AY34, Cibacron Brilliant Red 3B-A (Reactive Red 4) (Aldrich Chemical, Milwaukee, WI), Drimarene Brilliant Red X-2B (Reactive Red 56) (Pylam Products, Inc. Tempe, AZ), Levafix (registered trademark) Brilliant Red E-4B, Levafix Reactive dyes of various colors such as Brilliant Red F-6BA and similar Levafix dyes Dystar LP (Charlotte, NC Corporation), Procion (registered trademark) Red H8B (Reactive Red 31) (JCI America Corporation), Neozapon ( (Registered trademark) Red 492 (manufactured by BASF), Orasol (registered trademark) Red G (manufactured by Ciba-Geigy), Aizen (registered trademark) Spilon (registered trademark) RedC-BH (Hodogaya Chem ical Company), Spirit Fast Yellow 3G, Aizen Spilon Yellow C-GNH (manufactured by Hodogaya Chemical Company), Orasol Black RL (manufactured by Ciba-Geigy), Orasol Black RLP (manufactured by Ciba-Geigy), Savinyl Black RLS Oil-soluble dyes such as (made by Sandoz), Orasol Blue GN (made by Ciba-Geigy), Luxol BlueMBSN (made by Morton-Thiokol), Morfast (registered trademark) Black Concentrate A (made by Morton-Thiokol), and the like. These can be used individually or in combination of two or more kinds.

In the method of surface oxidation treatment described in Japanese Patent No. 4,464,081, in order to effectively generate functional groups such as a carboxyl group on the surface of carbon black particles, carbon black is treated with an oxidizing agent. As the oxidizing agent, for example, peroxodisulfates such as peroxodisulfate, peroxodiborate, peroxodicarbonate, and peroxodiphosphate can be used. As peroxodiacid, alkali metal salts are preferred. Or ammonium salts.

In the method described in Japanese Patent Publication No. 2008-517330, surface modification with an organic group having an ionic group is performed. Here, examples of the organic group include an arylene group, a heteroaryl group, or an alkylene group, and examples of the ionic group include a carboxylic acid group, a sulfonic acid group, an alkyl sulfate group, and an alkyl group. Amino or alkyl ammonium or a salt thereof.

As such, examples of the high-resistance carbon black include resin-coated carbon black, dye-coated carbon black, oxidation-treated carbon black, or carbon black surface-modified with an organic group having an ionic group. From the viewpoint of insulation properties, In terms of carbon black, resin-coated carbon black, dye-coated carbon black, and resin-coated carbon black are more preferred. These carbon blacks can be used in combination with high resistance treatment.

The carbon atom ratio in the surface composition of the high-resistance carbon black is preferably 95% or less, and more preferably 90% or less. On the other hand, the carbon atom ratio is usually 70% or more, preferably 80% or more, and more preferably 85% or more. By setting the carbon atom ratio in the surface composition of the high-resistance carbon black to be less than the above-mentioned upper limit value, there is a large effect of surface treatment, it is easy to increase the resistivity of the powder, and the volume resistance of the obtained pattern is likely to be a desired value. tendency. On the other hand, when the carbon atom ratio in the surface composition of the high-resistance carbon black is equal to or more than the above-mentioned lower limit value, the light-shielding property tends to be good. The combination of the upper limit and the lower limit is preferably 70 to 95%, more preferably 80 to 95%, and still more preferably 85 to 90%. The ratio of each atom in the surface composition of the high-resistance carbon black can be measured by X-ray photoelectron spectroscopy (XPS). More specifically, measurement can be performed using monochromatic AlKα 1,2-rays (1486.6 eV) as the excitation X-rays, setting the X-ray diameter to 1 mm, and the photoelectron flying angle to 90 °.

The volume resistivity of the high-resistance carbon black (d1) is not particularly limited, but is preferably 3 Ω · cm or more, more preferably 4 Ω · cm or more, still more preferably 5 Ω · cm or more, and even more preferably 6 Ω.・ Cm or more, particularly preferably 7 Ω · cm or more, and usually 100 Ω · cm or less, preferably 80 Ω · cm or less, more preferably 50 Ω · cm or less, and even more preferably 40 Ω · cm or less It is more preferably 30 Ω · cm or less, and even more preferably 20 Ω · cm or less. When it is more than the said lower limit, there exists a tendency for insulation property to improve.

The volume resistivity of the high-resistance carbon black (d1) can be measured by using a method described in Japanese Patent Laid-Open No. 2002-249678. A commercially available powder resistance measuring device such as MCP-PD51 type powder resistance measuring system manufactured by Mitsubishi Chemical ANALYTECH can also be used for measurement using a constant current application method. As a measurement procedure, first, a sample of about 2 g was placed in a Teflon (registered trademark) container having an inner diameter of 2 cm made of a brass electrode and a brass electrode was attached to the end. After the lid was closed, a load was applied by a tensile machine (Tensilon) at a speed of 0.2 mm / min, and it was held at 50 kg / cm ² for 1 minute, and then set to a current of 1 mA. The resistance was measured by a high-sensitivity tester. . In addition, the bulk resistivity of the powder under this load was calculated from the bulk thickness and resistance value of the powder by the following formula.

Volume resistivity (Ω ・ cm) = cross-sectional area of the powder (cm ² ) × resistance value (Ω) / bulk thickness of the powder (cm)

The volume resistivity of the high-resistance carbon black can also be estimated from the value of the volume resistivity of the cured film obtained by curing the photosensitive resin composition containing it. If the cured film (OD (optical per 1 μm film thickness) density (optical density) value: 3.3) The volume resistivity value is 1.0 × 10 ⁹ Ω · cm or more, it is presumed that BM with high resistance carbon black is used. As the method and conditions for measuring the volume resistivity, those described in the examples can be used.

The colorant (d) in the photosensitive resin composition of the present invention contains high-resistance carbon black (d1), and may further contain other colorants (d2). As other colorants, dyes or pigments can be used, and pigments are preferred in terms of heat resistance and light resistance.

As the pigment, pigments of various colors such as blue pigment, green pigment, red pigment, yellow pigment, purple pigment, orange pigment, brown pigment, and black pigment can be used. Further, as the structure, organic pigments such as azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, difluorene-based, indanthrene-based, and fluorene-based can be used In addition, various inorganic pigments can also be used.

Hereinafter, specific examples of pigments which can be used in the present invention are represented by pigment numbers. The terms "C.I. Pigment Red 2" and the like listed below refer to the dye index (C.I.). Examples of the red pigment include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Among them, preferred examples include CI Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, and 254. Further preferred examples include CI Pigment Red 177, 209, 224, and 254. .

Examples of the blue pigment include CI Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25 , 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78 , 79. Among them, preferably, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. Pigment Blue 15: 6. Examples of the green pigment include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Among them, preferred examples include C.I. Pigment Green 7, 36, and 58.

Examples of the yellow pigment include: CI Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. Among them, preferably, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and more preferably, C.I. Pigment Yellow 83, 138, 139, 150, 180.

Examples of the orange pigment include CI pigment orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among these, C.I. pigment oranges 38 and 71 are preferable.

Examples of the purple pigment include CI Pigment Violet 1, 1: 1,2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Among them, C.I. Pigment Violet 19 and 23 are preferred, and C.I. Pigment Violet 23 is further preferred.

When the photosensitive resin composition of the present invention is used in a light-shielding application such as a resin black matrix of a color filter, it is preferable to use a black colorant as another colorant. The black colorant can be used alone as a black colorant, or a mixture of red, green, and blue colorants can be used as the black colorant. These colorants can be appropriately selected from inorganic or organic pigments and dyes. Examples of colorants that can be mixed for the preparation of black colorants include Victoria Pure Blue (42595), Aumine O (41000), Cathilon Luminin (basic 13), and Rose Red 6GCP ( 45160), Rose B (45170), Saffron OK70: 100 (50240), Poppy X (42080), No. 120 / Leonor Yellow (21090), Leonor Yellow GRO (21090), Smeller Fast yellow 8GF (21105), benzidine yellow 4T-564D (21095), Smühler fast red 4015 (12355), Leonor 7B4401 (15850), fastogen blue TGR-L ( 74160), Leonor Blue SM (26150), Leonor Blue ES (Pigment Blue 15: 6), Lionon Red GD (Pigment Red 168), Leonor Green 2YS (Pigment Green 36) Etc. (Further, the numbers in () above refer to the dye index (CI)).

Furthermore, if other pigments that can be used in combination are indicated by CI numbers, for example, CI Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, CI Pigment Orange 36, 43, 51, 55, 59, 61, CI Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, CI Pigment Violet 19, 23, 29, 30, 37, 40, 50, CI Pigment Blue 15, 15: 1, 15: 4, 22, 60, 64, CI Pigment Green 7 , CI Pigment Brown 23, 25, 26 and so on.

Examples of the black colorant that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black. Among them, carbon black, acetylene black, graphite and other conductive black colorants can also be used to adjust the resistance value by mixing.

In addition, as the pigment, barium sulfate, lead sulfate, titanium oxide, yellow dandelion, iron dandelion, chromium oxide, and the like can also be used. These various pigments may be used in combination.

The average particle diameter of the pigment used in the present invention is not particularly limited as long as it can obtain the desired color development in the case of a colored layer, and it is different depending on the type of the pigment used. It is preferably in the range of 10 to 100 nm, and more preferably in the range of 10 to 70 nm. When the average particle diameter of the pigment is in the above range, the color characteristics of a liquid crystal display device manufactured using the photosensitive resin composition of the present invention can be made high-quality. The average particle diameter of the high-resistance carbon black is preferably 60 nm or less, more preferably 50 nm or less, and still more preferably 20 nm or more. By making it below the said upper limit, there exists a tendency for color characteristics, such as scattering suppression, to become favorable. Moreover, when it is more than the said lower limit value, there exists a tendency which can avoid that the quantity of a dispersing agent becomes excessive, and dispersibility becomes favorable easily. The average particle diameter of the pigment can be determined by a method of directly measuring the size of the primary particles from an electron microscope photograph. Specifically, the minor axis diameter and the major axis diameter of each primary particle are measured, and the average is taken as the particle diameter of the particle. Next, for 100 or more particles, the volume (mass) of each particle is approximated by a rectangular parallelepiped of the obtained particle diameter, and the volume average particle diameter is obtained, and this is taken as the average particle diameter. In addition, as an electron microscope, the same result can be obtained using either a transmission type (TEM) or a scanning type (SEM).

The photosensitive resin composition of the present invention may contain a dye as another colorant. Examples of the dyes that can be used in combination include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes. .

Examples of the azo dye include: CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, CI Mordant Black 7, and the like.

Examples of the anthraquinone dye include CI reduction blue 4, CI acid blue 40, CI acid green 25, CI reactive blue 19, CI reactive blue 49, CI disperse red 60, CI disperse blue 56, CI disperse blue 60 and so on. In addition, examples of the phthalocyanine dye include CI reduction blue 5 and the like, and examples of the quinone imine dye include CI basic blue 3 and CI basic blue 9. As the quinoline dye, for example, Examples include CI solvent yellow 33, CI acid yellow 3, CI disperse yellow 64, and the like. Examples of the nitro dye include CI acid yellow 1, CI acid orange 3, and CI disperse yellow 42.

(d) The content ratio of the colorant is not particularly limited, and it can be generally selected from the range of 1 to 70% by mass of the total solid content of the photosensitive resin composition. In this range, it is more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 40% by mass or more, even more preferably 45% by mass or more, and still more preferably 60% by mass or less. If it is more than the said lower limit value, there exists a tendency for light-shielding property to improve, and if it is below the said upper limit value, there exists a tendency for board | substrate adhesiveness to improve. The combination of the upper limit and the lower limit is preferably 20 to 60% by mass, more preferably 30 to 60% by mass, still more preferably 40 to 60% by mass, and even more preferably 45 to 60% by mass.

The content ratio of the high-resistance carbon black (d1) is not particularly limited, and it is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass in the total solid content of the photosensitive resin composition. Above, still more preferably 40% by mass or more, particularly preferably 45% by mass or more, most preferably 50% by mass or more, more preferably 70% by mass or less, and even more preferably 60% by mass or less. When it is more than the said lower limit value, there exists a tendency for it to become easy to have both light-shielding property and insulation, and when it is less than the said upper limit value, it is easy to have both substrate adhesiveness and insulation property. The combination of the upper limit and the lower limit is preferably 10 to 70% by mass, more preferably 20 to 70% by mass, still more preferably 30 to 60% by mass, even more preferably 40 to 60% by mass, and even more preferably 45 to 60% by mass. 60% by mass, preferably 50 to 60% by mass.

The content ratio of the carbon black constituting the high-resistance carbon black (d1) is not particularly limited, and it is preferably 20% by mass or more, more preferably 30% by mass or more, of all the solid components in the photosensitive resin composition, and more preferably It is preferably 40% by mass or more, particularly preferably 45% by mass or more, more preferably 60% by mass or less, more preferably 58% by mass or less, still more preferably 56% by mass or less, and even more preferably 54% by mass or less. If it is more than the said lower limit value, there exists a tendency for light-shielding property to improve, and if it is below the said upper limit value, there exists a tendency for board | substrate adhesiveness to improve. The combination of the upper limit and the lower limit is preferably 20 to 60% by mass, more preferably 30 to 58% by mass, still more preferably 40 to 56% by mass, and even more preferably 45 to 54% by mass.

In addition, the content ratio of the carbon black constituting the high-resistance carbon black (d1) in the colorant (d) is also not particularly limited. In the (d) colorant, it is preferably 60% by mass or more, and more preferably 80% by mass or more. It is more preferably 90% by mass or more, and usually 100% by mass or less. By setting it to be more than the said lower limit, there exists a tendency for light-shielding property and insulation property to improve.

When the content ratio of the carbon black constituting the high-resistance carbon black in the photosensitive resin composition is greater than or equal to the above lower limit value, a photosensitive resin composition having high light-shielding properties (optical density, OD value) can be obtained. There are variations depending on the high-resistance treatment method. In general, the content of the carbon black constituting the high-resistance carbon black is 38% by mass or more in the total solid content, so that the photosensitive resin of the present invention is used. When the composition forms a black matrix with a thickness of 1 μm, the optical density tends to be a value of 2.5 or more. When the composition is 47% by mass or more, the photosensitive resin composition of the present invention is used to form a thickness of 1 μm. In the case of a black matrix, the optical density tends to be a value of 3.0 or more. The optical density is more preferably 3.2 or more.

Furthermore, in the photosensitive resin composition, the content ratio of (d) the colorant is usually 20 to 500 parts by mass, preferably 30 to 400 parts by mass, and more preferably 100 parts by mass to (a) the alkali-soluble resin. The range is 40 to 350 parts by mass. When it is at least the above lower limit value, there is a tendency that it is easy to suppress a decrease in the solubility of the unexposed portion in the developer, and when it is at least the above upper limit value, it is easy to obtain a desired image film thickness. tendency.

<(E) Dispersant> In the present invention, in order to ensure the stability of quality, it is important to finely disperse (d) the colorant and stabilize the dispersion state, and therefore it is preferable to contain (e) a dispersant. As the dispersant, a polymer dispersant having a functional group is preferred, and in terms of dispersion stability, a carboxyl group; a phosphate group; a sulfonic acid group; or such bases; Or tertiary amine groups; quaternary ammonium bases; polymer dispersants derived from functional groups such as pyridine, pyrimidine, pyridine and other nitrogen-containing heterocyclic groups. Among them, particularly preferred is a polymeric dispersant having a primary, secondary or tertiary amine group; a quaternary ammonium base; a basic functional group derived from a nitrogen-containing heterocyclic group such as pyridine, pyrimidine, pyridine and the like. By using a polymer dispersant having such a basic functional group, there is a tendency that the dispersibility can be improved and a higher light-shielding property can be achieved.

Examples of the polymer dispersant include a urethane-based dispersant, an acrylic-based dispersant, a polyethylenimine-based dispersant, a polyallylamine-based dispersant, and a monomer containing an amine group. Macromonomer dispersant, polyoxyethylene alkyl ether dispersant, polyoxyethylene diester dispersant, polyether phosphoric acid dispersant, polyester phosphoric acid dispersant, sorbitan fatty acid ester dispersant , Aliphatic modified polyester-based dispersant.

As specific examples of such dispersants, examples of the product name include EFKA (registered trademark; manufactured by Efka Chemicals BV (EFKA)), Disperbyk (registered trademark; manufactured by BYK-Chemie), Disparlon (registered trademark; Kusumoto) (Manufactured by Kasei Corporation), SOLSPERSE (registered trademark; manufactured by Lubrizol), KP (made by Shin-Etsu Chemical Industry Co., Ltd.), Polyflow or Flowlen (registered trademark; manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark; manufactured by Ajinomoto Fine-Techno) )Wait. These polymer dispersants can be used singly or in combination of two or more kinds.

Among these, in terms of adhesiveness and linearity, the (e) dispersant is particularly preferably a urethane-based polymer dispersant and / or an acrylic polymer dispersant containing a basic functional group. . In terms of adhesion, a urethane-based polymer dispersant is particularly preferred. In terms of dispersibility and storage properties, a polymer dispersant having a basic functional group and having a polyester bond and / or a polyether bond is preferred.

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less, and more preferably 30,000 or less. By making it below the said upper limit, even if the content ratio of a coloring material is high, there exists a tendency for alkaline developability to become favorable. Examples of the urethane-based and acrylic polymer dispersants include: Disperbyk 160-167, 182 series (both urethane-based), Disperbyk 2000, 2001, etc. (both acrylic-based) (the above are all (By BYK-Chemie). Among the above-mentioned urethane-based polymer dispersants having a basic functional group and a polyester and / or polyether bond, a weight average molecular weight of 30,000 or less is particularly preferred, and examples thereof include Disperbyk167, 182, and the like.

<Urethane-based polymer dispersant> If a preferable chemical structure of a urethane-based polymer dispersant is specifically exemplified, for example, the polyisocyanate compound may have one or A compound having a number average molecular weight of 300 to 10,000 with two hydroxyl groups and a compound having active hydrogen and a tertiary amine group in the molecule are reacted to obtain a dispersion resin having a weight average molecular weight of 1,000 to 200,000.

Examples of the polyisocyanate compound include p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene-1,5- Aromatic diisocyanates such as diisocyanate, ditoluidine diisocyanate, hexamethylene diisocyanate, methyl imidate diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate And other aliphatic diisocyanates, isophorone diisocyanates, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω'-diisocyanate dimethylcyclohexane, and other alicyclic diisocyanates, xylylene Diisocyanate, α, α, α ', α'-tetramethylxylylene diisocyanate, aliphatic diisocyanates with aromatic rings, lysine triisocyanate, 1,6,11-undecane Triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-hexamethylenetriisocyanate, dicycloheptane triisocyanate, tris (isocyanate Phenylmethane), triisocyanate such as tris (isocyanatophenyl) thiophosphate, and terpolymers, water adducts and These polyol adducts and the like. As the polyisocyanate, a terpolymer of an organic diisocyanate is preferable, and a terpolymer of a toluene diisocyanate and a terpolymer of an isophorone diisocyanate are most preferable. These can be used alone or in combination of two or more.

As a method for producing the trimer of isocyanate, the following methods can be cited: using an appropriate trimerization catalyst, such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. Polyisocyanates are partially trimerized with isocyanate groups. After the trimerization is stopped by the addition of catalyst poison, the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the target isocyanurate. Polyester isocyanate.

Examples of compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule include polyether diol, polyester diol, polycarbonate diol, polyolefin diol, and the like An alkyl group of 1 to 25 is obtained by alkoxylating a single terminal hydroxyl group of these compounds and a mixture of two or more of these.

Examples of the polyether diol include polyether diol, polyether ester diol, and a mixture of two or more of these. Examples of the polyether glycol include those obtained by homopolymerizing or copolymerizing an alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polyoxytetramethylene glycol, and polyoxyhexamethylene. Methyl glycol, polyoxyoctamethylene glycol, and mixtures of two or more of these.

Examples of the polyether ester diols include those obtained by reacting an ether group-containing diol or a mixture with another diol with a dicarboxylic acid or an anhydride thereof, or by reacting an alkylene oxide with a polyester diol. Examples include poly (polyoxytetramethylene) adipate. As the polyether glycol, polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or an alkyl group having 1 to 25 carbon atoms is preferably used to alkoxylate the mono-terminal hydroxyl group of these compounds. Of compounds.

Examples of the polyester diol include a dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or the like. Anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol , 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2 , 2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8- Octanediol, aliphatic diols such as 2-methyl-1,8-octanediol, 1,9-nonanediol, alicyclic diols such as bis (hydroxymethyl) cyclohexane, benzyl alcohol, Those obtained by polycondensation of aromatic diols such as bis (hydroxyethoxy) benzene, N-alkyldialkanolamines such as N-methyldiethanolamine, etc., such as polyethylene adipate, polybutylene adipate Diesters, polyadipates, polyethylene / adipate, etc., or use the above diols or carbon number 1 to 25 Monoalcohol as an initiator to obtain a polylactone diol of the polylactone or mono alcohols such as polycaprolactone diol, poly-valerolactone, and mixtures of these two kinds or more. The polyester diol is preferably a polycaprolactone diol or a polycaprolactone diol or an alcohol having 1 to 25 carbon atoms as a starter.

Examples of the polycarbonate diol include poly (1,6-hexanedicarbonate) and poly (3-methyl-1,5-pentane) carbonate. Examples of the polyolefin diol include: Butadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, and the like. These can be used alone or in combination of two or more.

The number average molecular weight of the compound having one or two hydroxyl groups in the molecule is usually 300 to 10,000, preferably 500 to 6,000, and still more preferably 1,000 to 4,000. A compound having an active hydrogen and a tertiary amine group in the molecule used in the present invention will be described. Examples of active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom, include a hydrogen atom in a functional group such as a hydroxyl group, an amine group, and a thiol group. Among them, an amine group hydrogen atom is preferred. Especially preferred is a hydrogen atom of a primary amine group.

The tertiary amine group is not particularly limited, and examples thereof include an amine group or a heterocyclic structure having an alkyl group having 1 to 4 carbon atoms, and more specifically, an imidazole ring or a triazole ring. Examples of such compounds having active hydrogen and tertiary amine groups in the molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3- Propylene diamine, N, N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N -Diethylethylenediamine, N, N-dipropylethylenediamine, N, N-dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N- Diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1,4-butanediamine, and the like.

Examples of the nitrogen-containing heterocyclic ring when the tertiary amine group has a nitrogen-containing heterocyclic ring structure include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, and indene. Nitrogen-containing 5-membered heterocycles, such as azole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, pyridine ring, data ring, pyrimidine ring, tricyclic , Quinoline ring, acridine ring, isoquinoline ring and other nitrogen-containing 6-membered heterocyclic rings. Among these nitrogen-containing heterocyclic rings, an imidazole ring or a triazole ring is preferred.

Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, and 1- (2-aminoethyl) imidazole Wait. In addition, if a compound having a triazole ring and an amino group is specifically exemplified, 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3- Phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1 , 3,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole, and the like. Among these, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3 -Amino-1,2,4-triazole.

These can be used alone or in combination of two or more. As a preferred blending ratio of raw materials when producing a urethane-based polymer dispersant, a compound having a number average molecular weight of 300 to 10,000 with respect to 100 parts by mass of the polyisocyanate compound and having one or two hydroxyl groups in the molecule. 10 to 200 parts by mass, preferably 20 to 190 parts by mass, still more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass of a compound having active hydrogen and a tertiary amine group in the molecule, preferably 0.3 ～ 24 parts by mass.

The production of the urethane-based polymer dispersant is performed according to a known method for producing a urethane resin. As the solvent during production, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone and other ketones, ethyl acetate, butyl acetate, and acetic acid can be generally used. Esters such as sulphur, hydrocarbons such as benzene, toluene, xylene, hexane, diacetone alcohol, isopropanol, second butanol, third butanol, chlorides such as dichloromethane, chloroform, tetrahydrofuran , Aethers such as diethyl ether, aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethylsulfinium. These can be used alone or in combination of two or more.

In the above production, a urethane reaction catalyst is usually used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannous octoate; iron-based compounds such as iron acetoacetone and iron chloride; and triethylamine And three or more kinds of tertiary amines such as triethylene diamine and the like.

<Method for measuring amine value> The amine value of the dispersant is expressed by the mass of KOH in an amount equivalent to the alkali amount per 1 g of the solid content component except the solvent in the dispersant sample, and can be measured by the following method. In a 100 mL beaker, accurately weigh 0.5 to 1.5 g of the dispersant sample and dissolve it in 50 mL of acetic acid. Using an automatic titration device with a pH electrode, the solution was neutralized and titrated with a 0.1 mol / L HClO ₄ (perchloric acid) acetic acid solution. Using the inflection point of the titration pH curve as the end point of the titration, the amine value was obtained by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S) [where, W represents: the dispersant sample weighed [g], V represents: the titration at the end of the titration [mL], S Means: The solid content concentration of the dispersant sample [% by mass]] The amount of the compound having active hydrogen and tertiary amine group in the molecule is preferably controlled to 1 to 100 mgKOH / g in terms of the amine value after the reaction. range. A more preferable range is 5 to 95 mgKOH / g. The amine value is a value corresponding to the acid value by the titration of the basic amine group with an acid, expressed in mg of KOH. When the amine value is at least the above lower limit value, the dispersibility tends to be good, and when it is at most the above upper limit value, the developability tends to be good.

In addition, if the isocyanate group is left in the polymer dispersant by the above reaction and the isocyanate group is consumed by an alcohol or an amine compound, the stability of the product over time is high, so it is preferable. . The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. Especially preferred is below 30,000. When it is more than the said lower limit, dispersibility and dispersion stability tend to become favorable, and when it is below the said upper limit, there exists a tendency for solubility to become favorable. When the molecular weight is 30,000 or less, even when the content ratio of the colorant is particularly high, the alkaline developability tends to be good. Examples of such a particularly preferred commercially available urethane dispersant include Disperbyk 167, 182 (BYK-Chemie) and the like.

When the photosensitive resin composition of the present invention contains (e) a dispersant, the content ratio of the (e) dispersant is generally 50% by mass or less in the total solid content of the photosensitive resin composition, and is preferably 30 mass% or less, more preferably 20 mass% or less, usually 1 mass% or more, preferably 3 mass% or more, more preferably 5 mass% or more, still more preferably 7 mass% or more, and even more preferably 10 mass %the above. The combination of the upper limit and the lower limit is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, still more preferably 5 to 20% by mass, even more preferably 7 to 20% by mass, and even more preferably 10 -20% by mass. When it is at least the above-mentioned lower limit value, sufficient dispersibility tends to be easily ensured. When it is at least the above-mentioned upper limit value, the ratio of other components is not reduced, and it is easy to make color density, sensitivity, and film-forming property. The tendency to become full.

The content ratio of the dispersant is usually 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and usually 200 parts by mass or less with respect to 100 parts by mass of the colorant (d). It is 80 parts by mass or less, and more preferably 50 parts by mass or less. The combination of the upper limit and the lower limit is preferably 5 to 200 parts by mass, more preferably 10 to 80 parts by mass, and even more preferably 15 to 50 parts by mass. When it is at least the above-mentioned lower limit value, sufficient dispersibility tends to be easily ensured. When it is at least the above-mentioned upper limit value, the ratio of other components is not reduced, and it is easy to make color density, sensitivity, and film-forming property. The tendency to become full.

<Mercaptans> The photosensitive resin composition of the present invention preferably contains a thiol in order to improve the sensitivity and the adhesion to the substrate. Examples of the types of thiols include hexamethylene dithiol, sebacyl mercaptan, 1,4-dimethylmercaptobenzene, butanediol dimercaptopropionate, butanediol dimercaptoacetate, and ethylene glycol. Alcohol bismercaptoacetate, trimethylolpropane trimercaptoacetate, butanediol bismercaptopropionate, trimethylolpropane trimercaptopropionate, trimethylolpropane trimercaptoacetate, pentaerythritol Tetramercaptopropionate, pentaerythritol tetramercaptoacetate, trimercapto trimercaptopropionate, ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate) (abbreviated as PGMB) , Butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane (trade name: Karenz MT BD1, manufactured by Showa Denko Corporation), butanediol trimethylol Propanetris (3-mercaptobutyrate), pentaerythritol tetra (3-mercaptobutyrate) (trade name: Karenz MT PE1, manufactured by Showa Denko Corporation), pentaerythritol tri (3-mercaptobutyrate), ethylene glycol Bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tri (3-mercaptoisobutyrate), trimethylolpropane tri (3-mercaptoisobutyrate) Mercaptobutyrate) (abbreviated as TPMB), three Methylolpropane tris (2-mercaptoisobutyrate) (TPMIB for short), 1,3,5-tris (3-mercaptobutoxyethyl) -1,3,5-tri-2,4, 6 (1H, 3H, 5H) -trione (trade name: Karenz MT NR1, manufactured by Showa Denko Corporation), etc. These can be used alone or in combination of two or more. Polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1 are preferred. Among them, Karenz MT BD1, Karenz MT PE1, Karenz MT NR1 are more preferred, and Karenz MT NR1 is particularly preferred. PE1.

In the case of using a thiol compound, the content ratio of the thiol compound is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably in the total solid content of the photosensitive resin composition of the present invention. It is 0.5% by mass or more, usually 10% by mass or less, and preferably 5% by mass or less. When it is more than the said lower limit value, there exists a tendency which can suppress the fall of sensitivity, and when it is less than the said upper limit value, there exists a tendency for the storage stability to become easy easily.

<Solvent> The photosensitive resin composition of the present invention is generally composed of (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, (d) a colorant, and various components used as necessary. Use in a state of being dissolved or dispersed in an organic solvent. As the organic solvent, a boiling point (under the conditions of a pressure of 1013.25 [hPa]; hereinafter, the same about the boiling point) is preferably selected in the range of 100 to 300 ° C. More preferred is a solvent having a boiling point of 120 to 280 ° C. Examples of such an organic solvent include the following.

Such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol third butyl ether, Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, Glycol monoalkyl ethers of 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

Such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether Glycol dialkyl ethers; such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether Diethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl Ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol Alcohol monoether acetates, glycol alkyl ether acetates of 3-methyl-3-methoxybutyl acetate;

Diethylene glycol diacetates such as ethylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanediol diacetate; alkyl acetates such as cyclohexanol acetate Classes; such as pentyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, dihexyl ether; such as acetone, methyl ethyl ketone, methyl Amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butan Ketones of methylketone, methylhexylketone, methylnonylketone, methoxymethylpentanone; such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol , Diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, benzyl alcohol or polyhydric alcohols; such as n-pentane, n-octane, diisobutylene, n-hexane, hexene , Aliphatic hydrocarbons such as isoprene, dipentene, dodecane; such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexane;

Such as benzene, toluene, xylene, cumene aromatic hydrocarbons; such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene Alcohol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octoate, butyl stearate, ethyl benzoate, 3-ethyl Methyloxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methylpropionate Chain or cyclic esters of butyloxypropionate and γ-butyrolactone; such as alkoxycarboxylic acids of 3-methoxypropionic acid and 3-ethoxypropionic acid;

For example, halogenated hydrocarbons such as chlorobutane and chloropentane; for example, ether ketones of methoxymethylpentanone; for example, nitriles of acetonitrile and benzonitrile; etc. As commercially available solvents equivalent to the above, enumerated: Mineral spirit, Varsol # 2, Apco # 18 Solvent, Apco Thinner (Apco thinner), Socal Solvent No. 1 and No. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl card Bisalcohol, butylcarbitol, methyl cyrus ("Salox" is a registered trademark; the same below), ethyl cyrus, ethyl cyrus, acetate cyrus, diethyl acetate Dimethyl glycol (both trade names) and the like.

These organic solvents may be used alone or in combination of two or more. When a pixel or a black matrix of a color filter is formed by a photolithography method, as the organic solvent, a boiling point in a range of 100 to 250 ° C is preferably selected. More preferably, it has a boiling point of 120 to 230 ° C. Among the above-mentioned organic solvents, glycol alkyl ether acetates are preferred in terms of excellent balance of coatability, surface tension, and the like, and high solubility of constituent components in the composition.

The glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As other organic solvents that can be used in combination, glycol monoalkyl ethers are particularly preferred. Among these, propylene glycol monomethyl ether is preferred in terms of the solubility of the constituents in the composition. Furthermore, glycol monoalkyl ethers have high polarity. If the amount is too large, the pigment tends to agglomerate, which leads to a decrease in storage stability such as an increase in the viscosity of the photosensitive resin composition to be obtained later. The ratio of the diol monoalkyl ethers is preferably 5 to 30% by mass, and more preferably 5 to 20% by mass.

It is also preferable to use an organic solvent having a boiling point of 200 ° C. or higher (hereinafter sometimes referred to as a “high boiling point solvent”). By using such a high-boiling-point solvent in combination, the photosensitive resin composition does not easily dry out, but has the effect of preventing the uniform dispersion state of the pigment in the composition from being damaged by rapid drying. That is, for example, there is an effect of preventing foreign matter defects due to precipitation and solidification of a colorant or the like at the end of the slit nozzle. From the standpoint of this effect, among the various solvents mentioned above, dipropylene glycol methyl ether acetate, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred. 4-butanediol diacetate, 1,3-butanediol diacetate, glycerol triacetate, 1,6-hexanediol diacetate.

When a high boiling point solvent is used in combination, the content ratio of the high boiling point solvent in the organic solvent is preferably 0% to 50% by mass, more preferably 0.5% to 40% by mass, and even more preferably 1% to 30% by mass. %. By setting it to be above the lower limit value, for example, there is a tendency that foreign matter defects caused by the precipitation and curing of the color nozzle and the like at the end of the slit nozzle can be suppressed, and by setting it to be less than the above upper limit value, the composition can be suppressed The drying speed becomes too slow, and it is easy to avoid the problem that the production pressure of the vacuum drying process in the color filter manufacturing step is poor, or the problem of pre-baked porosity is caused.

In the photosensitive resin composition of the present invention, the content ratio of the organic solvent is not particularly limited. From the standpoint of ease of coating or viscosity stability, the total solid content in the photosensitive resin composition is preferred. 5 mass% or more, more preferably 8 mass% or more, still more preferably 10 mass% or more, still more preferably 40 mass% or less, more preferably 30 mass% or less, and still more preferably 25 mass% or less, It is particularly preferable to adjust the liquid in a manner of 20% by mass or less. The combination of the upper limit and the lower limit is preferably 5 to 40% by mass, more preferably 8 to 30% by mass, still more preferably 10 to 25% by mass, and even more preferably 10 to 20% by mass.

<Other Formulation Ingredients of Photosensitive Resin Composition> In the photosensitive resin composition of the present invention, in addition to the above-mentioned components, a close adhesion improver, a coatability improver, a pigment derivative, a development improver, and an ultraviolet absorber can be appropriately blended. , Antioxidants, etc.

<Adhesive Elevator> In order to improve the adhesiveness with the substrate, an adhesive enhancer may be contained, and examples thereof include a silane coupling agent, a titanium coupling agent, and the like, and a silane coupling agent is particularly preferred. Examples of such silane coupling agents include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, and X-12-1050 (made by Shin-Etsu Silicones) , Z-6040, Z-6043, Z-6062 (manufactured by Dow Corning Toray). Furthermore, one type of silane coupling agent may be used, or two or more types may be used in any combination and ratio. Furthermore, the photosensitive resin composition of the present invention may contain an adhesion promoter other than a silane coupling agent, and examples thereof include a phosphoric acid-based adhesion promoter and other adhesion promoters.

As the phosphoric acid-based adhesion promoter, a (meth) acryloxy group-containing phosphate ester is preferable, and among them, those represented by the following general formulae (g1), (g2), and (g3) are preferred.

[Chemical 19]

In the general formulae (g1), (g2), and (g3), R ⁵¹ each independently represents a hydrogen atom or a methyl group. l and l 'each independently represent an integer of 1 to 10, and m each independently represents 1, 2 or 3. Examples of other adhesion-promoting agents include TEGO (registered trademark) Add Bond LTH (manufactured by Evonik). These phosphate-containing compounds or other adhesives can also be used alone or in combination of two or more.

The content ratio of the adhesion-improving agent in the photosensitive resin composition is not particularly limited, but it is preferably 0.01% by mass or more, more preferably 0.10% by mass or more, and further preferably 0.50% by mass or more in all the solid components. It is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, still more preferably 2.0% by mass or less, and even more preferably 1.5% by mass or less. When it is more than the said lower limit value, there exists a tendency for adhesive force to improve, and when it is below the said upper limit value, there exists a tendency for developability to become favorable.

<Coatability Enhancer> In order to improve coatability, a surfactant may be contained in the photosensitive resin composition of the present invention as a coatability enhancer. As the surfactant, for example, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among them, non-ionic surfactants are preferred because they are less likely to adversely affect various properties. Among them, fluorine-based or polysilicon are effective in terms of coating properties. An oxygen-based surfactant.

Examples of such a surfactant include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by NEOS), BYK-300, BYK-325, BYK-330 (by BYK-Chemie), and KP340 ( (Made by Shin-Etsu Silicones), MEGAFAC F-470, F-475, F-478, F-554, F-559 (made by DIC), SH7PA (made by Dow Corning Toray), DS-401 (made by Daikin) ), L-77 (manufactured by Nippon Unicar) and FC4430 (manufactured by 3M Japan). Furthermore, one type of surfactant may be used, or two or more types may be used in any combination and ratio. In the case where the photosensitive resin composition of the present invention contains a surfactant, the content ratio of the surfactant in the photosensitive resin composition is not particularly limited, and it is preferably among all solid components of the photosensitive resin composition. 0.01 mass% or more, more preferably 0.05 mass% or more, more preferably 1.0 mass% or less, more preferably 0.7 mass% or less, still more preferably 0.5 mass% or less, and even more preferably 0.3 mass% or less. When it is more than the said lower limit value, there exists a tendency for coating uniformity to become favorable, and when it is below the said upper limit value, there exists a tendency for it to become easy to suppress a fall of sensitivity. The combination of the upper limit and the lower limit is preferably 0.01 to 1.0% by mass, more preferably 0.01 to 0.7% by mass, still more preferably 0.05 to 0.5% by mass, and even more preferably 0.05 to 0.3% by mass.

<Pigment derivative> A pigment derivative may be contained in the photosensitive resin composition of the present invention in order to improve dispersibility and storage stability. Examples of the pigment derivative include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, difluorene-based, anthraquinone-based, and indigo Derivatives such as the Shihlin system, the hydrazone system, the hydrazone system, the pyrrolopyrrole dione system, and the difluorene system. Among them, phthalocyanine system and quinophthalone system are preferred.

Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamido group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylamino group, a hydroxyl group, a carboxyl group, and a fluorenyl group. Those which are bonded to the pigment skeleton directly or via an alkyl group, an aryl group, a heterocyclic group and the like are preferably a sulfonic acid group. Moreover, a plurality of these substituents may be substituted on one pigment skeleton. Specific examples of the pigment derivative include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, and pyrrolopyrrole Sulfonic acid derivatives of ketones, sulfonic acid derivatives of difluorene, and the like. These can be used alone or in combination of two or more. The pigment derivative is preferably used together with a dispersant.

In the case where the photosensitive resin composition of the present invention contains a pigment derivative, the content ratio of the pigment derivative in the photosensitive resin composition is not particularly limited, and it is preferably among all solid matter components of the photosensitive resin composition. 0.1 mass% or more, more preferably 0.5 mass% or more, still more preferably 1.0 mass% or more, still more preferably 10 mass% or less, and even more preferably 5 mass% or less. When it is more than the said lower limit, there exists a tendency for dispersion stability to improve, and when it is less than the said upper limit, there exists a tendency for developability to become favorable. The combination of the upper limit and the lower limit is, for example, preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and even more preferably 1.0 to 5% by mass.

<Physical properties of photosensitive resin composition> The photosensitive resin composition of the present invention can be preferably used for forming a black matrix, and from this viewpoint, it is preferably black. In addition, the optical density (OD) per 1 μm of the thickness of the cured film is preferably 1.0 or more, more preferably 2.0 or more, even more preferably 2.5 or more, even more preferably 3.0 or more, and even more preferably 4.0 or more. It is preferably 4.5 or more, and usually 6.0 or less. By setting it to be more than the said lower limit, there exists a tendency for sufficient light shielding property to be ensured.

<The manufacturing method of a photosensitive resin composition> The photosensitive resin composition of this invention can be manufactured according to a conventional method. In general, (d) the colorant is preferably dispersed in advance using a paint conditioner, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. (D) The coloring material is micronized by the dispersion treatment, so that the coating characteristics of the photosensitive resin composition are improved. In addition, when a black colorant is used as the (d) colorant, it contributes to improving the light shielding ability.

The dispersion treatment is usually preferably performed in a system in which a part or the whole of (d) a colorant, an organic solvent, and (e) a dispersant, and (a) an alkali-soluble resin are used in combination (hereinafter sometimes used for dispersion treatment). The mixture and the composition obtained by this treatment are called "ink" or "pigment dispersion"). In particular, if a polymer dispersant is used as the dispersant, it is preferable that the obtained ink and the photosensitive resin composition are inhibited from thickening with time (excellent in dispersion stability). Furthermore, in the case of performing a dispersion treatment on a liquid containing all the components formulated in the photosensitive resin composition, there is a possibility that a highly reactive component may be modified due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.

In the case where the (d) colorant is dispersed by a sand mill, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm can be preferably used. As the conditions for the dispersion treatment, the temperature is usually in the range of 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. As the dispersing time, there are different suitable times depending on the composition of the liquid and the size of the dispersing processing device, etc., so it is appropriately adjusted. The standard for dispersion is to control the gloss of the ink so that the 20-degree specular gloss of the photosensitive resin composition (JIS Z8741) is in the range of 100 to 200. When the gloss of the photosensitive resin composition is low, the dispersion treatment is insufficient, and rough pigment (colorant) particles are often left, and the developability, adhesion, and resolution are insufficient. possibility. In addition, if the dispersing treatment is performed until the gloss value exceeds the above-mentioned range, the pigment is broken and a large amount of ultrafine particles are generated. Therefore, the dispersion stability tends to be deteriorated.

Next, the ink obtained by the above dispersion treatment is mixed with the other components contained in the photosensitive resin composition to prepare a uniform solution. In the production steps of the photosensitive resin composition, it is often the case that fine dirt is mixed in the liquid, and therefore it is more desirable to perform a filtration treatment on the obtained photosensitive resin composition by a filter or the like.

[Hardened product] The hardened product of the present invention is obtained by hardening the photosensitive resin composition of the present invention. The cured product obtained by curing the photosensitive resin composition can be preferably used as a member constituting a color filter such as a pixel, a black matrix, and a colored spacer.

[Black Matrix] The black matrix of the present invention containing the hardened product of the present invention or the color filter including the black matrix of the present invention will be described according to the manufacturing method thereof.

(1) Support As a support for forming a black matrix, the material is not particularly limited as long as it has a moderate strength. Transparent substrates are mainly used. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, and polyfluorene. Thermosetting resin sheets such as thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, poly (meth) acrylic resins, and various glasses. Among them, glass and a heat-resistant resin are preferred from the viewpoint of heat resistance. In addition, transparent electrodes such as ITO (Indium Tin Oxides) and IZO (Indium Zinc Oxide) may be formed on the surface of the substrate. In addition to a transparent substrate, it can also be formed on a thin-film transistor (thin-film transistor) array.

In order to improve surface properties such as adhesion, the support may be subjected to a corona discharge treatment, an ozone treatment, an atmospheric piezoelectric slurry treatment, a thin film forming treatment of various resins such as a silane coupling agent or a urethane resin, etc., as necessary. The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. When a thin film forming process is performed on various resins, the film thickness is usually in the range of 0.01 to 10 μm, and preferably in the range of 0.05 to 5 μm.

(2) Black matrix In order to form the black matrix of the present invention by using the photosensitive resin composition of the present invention, a photosensitive substrate of the present invention is coated on a transparent substrate and dried, and then a photomask is placed on the sample. , Image exposure and development are performed through the photomask, and thermal hardening or light hardening is performed as necessary to form a black matrix.

(3) Formation of black matrix (3-1) Coating of photosensitive resin composition The coating of the photosensitive resin composition for black matrix on a transparent substrate can be performed by a spin coating method, a wire rod coating method, or a flow coating method. Method, die coating method, roll coating method, spray coating method, or the like. Among them, according to the die coating method, the amount of coating liquid used can be greatly reduced, and there is no effect of fog or the like attached when the spin coating method is used, and the generation of foreign matter is suppressed. From such a comprehensive point of view, it is preferable.

The thickness of the coating film is generally in the range of 0.2 to 10 μm, more preferably in the range of 0.5 to 6 μm, and even more preferably in the range of 1 to 4 μm, based on the film thickness after drying. By making it below the said upper limit value, there exists a tendency for pattern development to become easy, and gap adjustment in a liquid crystal cell formation process also becomes easy. When it is more than the above-mentioned lower limit value, there is a tendency that a desired color is easily developed.

(3-2) Drying of the coating film The drying of the coating film after the photosensitive resin composition is coated on the substrate is preferably a drying method using a hot plate, an IR (infrared radiation) oven or a convection oven. The drying conditions can be appropriately selected according to the type of the above-mentioned solvent components, the performance of the dryer used, and the like. The drying time is generally selected within a temperature range of 40 to 200 ° C and 15 seconds to 5 minutes according to the type of the solvent component and the performance of the dryer used, and is preferably a temperature of 50 to 130 ° C and 30 seconds to Choose within 3 minutes.

The higher the drying temperature is, the higher the adhesion of the coating film to the transparent substrate is. However, if the drying temperature is too high, the alkali-soluble resin may be decomposed and thermal polymerization may be initiated, resulting in poor development. In addition, the drying step of the coating film may be a reduced-pressure drying method for drying in a reduced-pressure chamber without increasing the temperature.

(3-3) Exposure Image exposure is performed by superposing a negative mask pattern on the coating film of the photosensitive resin composition, and irradiating light with a wavelength from the ultraviolet region to the visible region through the mask pattern. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being reduced due to oxygen, an oxygen blocking layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable coating film and then exposed. The light source used in the image exposure is not particularly limited. Examples of the light source include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and carbon arc lamps. In the case of using light of a specific wavelength, an optical filter may be used.

(3-4) Development of the black matrix of the present invention can be produced by: after the image exposure of the coating film formed of the photosensitive resin composition by the light source described above, by using an organic solvent or containing a surfactant and an alkali An aqueous solution of a chemical compound is developed to form an image on a substrate. The aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye, or a pigment.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Inorganic basic compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, or mono, di or triethanolamine, mono, di or trimethylamine, mono, di or tri Organics such as ethylamine, mono- or diisopropylamine, n-butylamine, mono-, di-, or tri-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline Basic compounds. These basic compounds may also be a mixture of two or more.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. Anionic surfactants such as nonionic surfactants, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkylsulfonates, sulfosuccinates, etc. , Alkyl betaines, amino acids and other amphoteric surfactants.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cyrus, butyl cyrus, phenyl cyrus, propylene glycol, and diacetone alcohol. The organic solvent may be used alone or in combination with an aqueous solution. The conditions for the development process are not particularly limited. Usually, the development temperature is in the range of 10 to 50 ° C. Among them, 15 to 45 ° C is preferred, and 20 to 40 ° C is particularly preferred. The development method may be a dip development method, a spray development method, or a coating method. Any one of a brush development method and an ultrasonic development method.

(3-5) Thermal curing treatment The substrate after development is subjected to a thermal curing treatment or a light curing treatment, preferably a thermal curing treatment. As the heat curing treatment conditions at this time, the temperature is selected in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is selected in the range of 5 to 60 minutes. The height of the black matrix formed in the above manner is usually 0.5 to 5 μm, preferably 0.8 to 4 μm. Furthermore, the optical density (OD) per thickness of 1 μm is 2.0 or more, preferably 2.5 or more, more preferably 3.0 or more, and even more preferably 3.2 or more.

On a transparent substrate provided with a black matrix, a photosensitive resin composition containing a colorant of one of red, green, and blue colors is coated in the same process as in (3-1) to (3-5) above. After being dried, a photomask is superimposed on the coating film, and image exposure and development are performed through the photomask. If necessary, a pixel image is formed by heat curing or light curing to produce a colored layer. This operation is performed separately for the photosensitive resin compositions of three colors of red, green, and blue, thereby forming a color filter image. The order of these is not limited to the above.

In addition to the black matrix, the photosensitive resin composition of the present invention can also be used as a photosensitive resin composition for colored spacers. When a spacer is used in a TFT LCD (liquid crystal display, liquid crystal display device), there may be a case where a TFT which is a switching element malfunctions due to light incident on the TFT. The colored spacer is used to prevent this. For example, Japanese Patent Laid-Open No. 8-234212 describes making the spacer light-shielding. The colored spacers can be formed by the same method as the black matrix except that a mask for the colored spacers is used.

(3-6) Formation of transparent electrodes A color filter can be used to form transparent electrodes such as ITO on the image in the original state. It is used as a part of parts such as color displays and liquid crystal display devices, but to improve surface smoothness. Or durability, if necessary, a top coat such as polyimide or polyimide can be provided on the image. In addition, there are cases where a transparent electrode is not formed in a use such as a planar alignment driving method (IPS (In Plane Switching) mode).

[Image display device] The image display device of the present invention is a person having the cured product of the present invention, and examples thereof include those having the black matrix of the present invention. The image display device is not particularly limited as long as it is an image or video display device, and examples thereof include a liquid crystal display device and an organic EL display described below.

[Liquid crystal display device] The liquid crystal display device of the present invention has the black matrix of the present invention described above, and the formation order or formation position of the color pixels or the black matrix is not particularly limited.

Liquid crystal display devices usually form an alignment film on a color filter. After the spacers are dispersed on the alignment film, they are bonded to a counter substrate to form a liquid crystal cell. Liquid crystal is injected into the formed liquid crystal cell and connected to a counter electrode. And done. The alignment film is preferably a resin film such as polyimide. The alignment film is usually formed by a gravure printing method and / or a flexographic printing method, and the thickness of the alignment film is tens of nanometers. After the hardening treatment of the alignment film is performed by thermal calcination, the surface treatment is performed by the irradiation of ultraviolet rays or the treatment with an abrasive cloth, and the surface state of the tilt of the liquid crystal can be adjusted by processing.

As the spacer, a size suitable for the gap (gap) with the opposing substrate is used, and usually, it is preferably 2 to 8 μm. A photoresist method can also be used to form a photosensitive spacer (PS) of a transparent resin film on a color filter substrate, and it can be effectively used instead of the spacer. As the counter substrate, an array substrate is generally used, and a TFT (thin film transistor) substrate is particularly preferred.

The gap between the substrate and the opposing substrate varies depending on the application of the liquid crystal display device, and is usually selected within a range of 2 to 8 μm. After bonding to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is hardened by UV irradiation and / or heating to seal the periphery of the liquid crystal cell. For the liquid crystal cell sealed around, after cutting into a panel unit, pressurize it in a vacuum chamber, immerse the liquid crystal injection port in the liquid crystal, and then release the liquid crystal into the liquid crystal cell. The degree of pressure reduction in the liquid crystal cell is usually 1 × 10 ^-2 to 1 × 10 ^-7 Pa, and preferably 1 × 10 ^-3 to 1 × 10 ^-6 Pa. The liquid crystal cell is preferably heated under reduced pressure, and the heating temperature is usually 30 to 100 ° C, and more preferably 50 to 90 ° C. The heating during the pressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. For a liquid crystal cell into which liquid crystal is injected, a liquid crystal injection port is sealed by curing a UV curing resin, thereby completing a liquid crystal display device (panel).

The type of the liquid crystal is not particularly limited, and may be a conventionally known liquid crystal such as an aromatic system, an aliphatic system, or a polycyclic compound, and may be any of a lyotropic liquid crystal and a thermotropic liquid crystal. As the thermotropic liquid crystal, a nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, and the like are known, and any of them may be used.

[Organic EL Display] The organic EL display of the present invention is produced using the color filter of the present invention.

When an organic EL display is manufactured using the color filter of the present invention, for example, as shown in FIG. 1, first, a pattern formed by a photosensitive resin composition is formed on a transparent support substrate 10 (that is, pixels 20). And a color filter formed of a resin black matrix (not shown) provided between adjacent pixels 20 and an organic light-emitting body 500 laminated on the color filter via an organic protective layer 30 and an inorganic oxide film 40, and This can produce an organic EL element 100. In addition, at least one of the pixel 20 and the resin black matrix was produced using the photosensitive resin composition of the present invention. As a method for stacking the organic light emitting body 500, a method of forming a transparent anode 50, a hole injection layer 51, a hole transmission layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 in this order on the upper surface of the color filter may be cited. , Or a method in which an organic light-emitting body 500 formed on another substrate is bonded to the inorganic oxide film 40. The organic EL device 100 thus produced can be used to produce an organic EL device by, for example, the method described in "Organic EL Display" (Ohmsha, Inc., released on August 20, 2004, at the time by Jing Shi, Anda Chiba, and Hideki Murata) EL display.

Furthermore, the color filter of the present invention can be applied to an organic EL display of a passive driving method, and can also be applied to an organic EL display of an active driving method. [Example]

Next, the present invention will be described more specifically by citing synthesis examples, examples, and comparative examples. However, the present invention is not limited to the following examples as long as the gist is not exceeded. The volume resistivity of the colorant is measured in the following procedure.

(Measurement of volume resistivity of colorant) First, a sample of about 2 g was placed in a Teflon (registered trademark) container with an inner diameter of 2 cm and a brass electrode was mounted on the lower part. After the lid of the electrode is made of a Teflon rod, a load is applied at a speed of 0.2 mm / min by a tensile machine, and it is held at 50 kg / cm ² for 1 minute, and then set to a current of 1 mA. Measure the resistance. The volume resistivity of the powder (colorant) under this load was calculated from the bulk thickness and the resistance value by the following formula.

Volume resistivity (Ω ・ cm) = cross-sectional area of the powder (cm ² ) × resistance value (Ω) / bulk thickness of the powder (cm)

<Preparation of coated carbon black 1> The coated carbon black 1 was prepared by the method described in Production Example 1 of Japanese Patent Laid-Open No. 2013-195538. As the carbon black, MA77 (manufactured by Mitsubishi Chemical Corporation, carbon black) was used.

<Preparation of coated carbon black 2> 100 g of carbon black MA77 (manufactured by Mitsubishi Chemical Corporation, carbon black) was put into a cylindrical kiln with an inner diameter of 10 cm and a length of 10 cm, and was rotated at 9 rpm while rotating Surface oxidation treatment was performed by contacting a mixed gas of air and ozone (ozone 6000 ppm) for 3 hours. Then, 60 g of the carbon black was dispersed in 1300 g of pure water. Furthermore, 1.1 g of a hardener (IBMI12 (manufactured by Mitsubishi Chemical Corporation)) was added to a resin solution (jER154 (manufactured by Mitsubishi Chemical Corporation): 5.6 g, toluene: 60 mL) dissolved in toluene. After being sufficiently dissolved, water 600 was added. 120 mL of ethanol and 120 mL of ethanol were stirred by a homogenizer at 9000 rpm for 30 minutes to prepare a resin emulsion. Then, the above-mentioned resin emulsion was slowly added to the carbon black dispersion liquid stirred with a screw, and the surface of the carbon black was treated with a resin. In addition, heating was performed while maintaining stirring, and toluene was evaporated, followed by hardening treatment at 70 ° C for 4 hours. After filtering off the water, it was placed in a vacuum drying container and dried at 62 ° C. for 10 hours. The water and the solvent were removed to obtain a coated carbon black 2. Furthermore, the volume resistivity of the coated carbon black 2 was measured based on the above (measurement of the volume resistivity of the colorant), and the result was 15.33 Ω · cm.

<Preparation of coated carbon black ink 1> Using the coated carbon black 1 prepared according to the above <preparation of coated carbon black 1>, a solid was prepared by the method described in Production Example 2 of Japanese Patent Laid-Open No. 2013-195538. 25% by mass of coated carbon black ink 1. In addition, as a dispersant, DISPERBYK-167 (manufactured by BYK-Chemie, a basic urethane dispersant) was used.

The quality of each component of the obtained coated carbon black ink 1 is shown below.・ Pigment / MA77 (manufactured by Mitsubishi Chemical Corporation, carbon black): 18.0 parts by mass ・ Coating resin / jER (registered trademark) 828 (manufactured by Mitsubishi Chemical Corporation, epoxy resin): 2.0 parts by mass ・ Dispersant / DISPERBYK-167 (BYK -Manufactured by Chemie, basic urethane dispersant): 4.4 parts by mass • Dispersion aid (pigment derivative) / Solsperse 12000 (made by Lubrizol, phthalocyanine pigment derivative with acidic group): 1.0 part by mass・ Solvent / propylene glycol monomethyl ether acetate (PGMEA): 76.2 parts by mass

<Preparation of Coated Carbon Black Ink 2> Except that in the above <Preparation of Carbon Black Ink 1>, the coated carbon black 2 prepared in accordance with the above <Preparation of Carbon Black 2> is used in place of the coated carbon black 1, and Preparation of carbon black ink 1> Coated carbon black ink 2 was prepared in the same order.

<Preparation of carbon black ink> Except for the above-mentioned <Preparation of coated carbon black ink 1>, MA77 (manufactured by Mitsubishi Chemical Corporation, carbon black) 18.0 parts by mass is used instead of coated carbon black 20.0 parts by mass (carbon black 18.0 parts by mass, coated resin Except for 2.0 parts by mass), the carbon black ink 3 was prepared in the same procedure as in the <Preparation of the coated carbon black ink 1>. Furthermore, the volume resistivity of MA77 was measured based on the above (measurement of the volume resistivity of the colorant), and the result was 1.69 Ω · cm.

<Synthesis example 1: Synthesis of alkali-soluble resin (1)>

[Chemical 20]

50 g of epoxy compound (epoxy equivalent 264) of the above structure, 13.65 g of acrylic acid, 60.5 g of 3-methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of p-methoxyphenol were charged into a thermometer. In a flask of a stirrer, a cooling tube, while stirring, react at 90 ° C until the acid value becomes 5 mgKOH / g or less. The reaction required 12 hours to obtain an epoxy acrylate solution. 25 parts by mass of the obtained epoxy acrylate solution, 0.76 parts by mass of trimethylolpropane (TMP), 3.3 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 3.5 parts by mass of tetrahydrophthalic anhydride (THPA) Put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and slowly raise the temperature to 105 ° C while stirring while reacting. When the resin solution becomes transparent, it is diluted with 3-methoxybutyl acetate (MBA) and prepared so that the solid content becomes 50% by mass. An acid value of 115 mgKOH / g and a polystyrene conversion measured by GPC are obtained. The alkali-soluble resin (1) having a weight average molecular weight (Mw) of 2600.

<Synthesis Example 2: Synthesis of Alkali-Soluble Resin (2)>

[Chemical 21]

7.3 g of epoxy compound (epoxy equivalent 240) of the above chemical structure, 2.2 g of acrylic acid, 6.4 g of propylene glycol monomethyl ether acetate, 0.18 g of tetraethylammonium chloride, and 0.007 g of p-methoxyphenol In a flask with a thermometer, a stirrer, and a cooling tube, the reaction was performed at 100 ° C while stirring until the acid value became 5 mgKOH / g or less. The reaction required 9 hours to obtain an epoxy acrylate solution. 16 parts by mass of the obtained epoxy acrylate solution, 0.4 parts by mass of trimethylolpropane (TMP), 3.5 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 0.06 parts by mass of tetrahydrophthalic anhydride (THPA) And 14 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was gradually raised to 105 ° C. while stirring, and reacted to obtain a solid content of 40% by mass, Alkali-soluble resin (2) having an acid value of 100 mgKOH / g and a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC of 10,400.

<Photopolymerization initiator (1)>

[Chemical 22]

As the photopolymerization initiator (1), a compound having the above-mentioned structure synthesized by the method described in International Publication No. 2015/036910 is used.

<Photopolymerization initiator (2)>

[Chemical 23]

As the photopolymerization initiator (2), TR-PBG-304 manufactured by Changzhou Qiangli Electronics Co., Ltd. having the above structure was used.

<Photopolymerization initiator (3)>

[Chemical 24]

As the photopolymerization initiator (3), OXE-01 manufactured by BASF Corporation having the above-mentioned structure was used.

<Photopolymerizable monomer> As the photopolymerizable monomer, KAYARAD DPHA (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Nippon Kayaku Co., Ltd. was used.

<Adhesive Elevator> KBM-5103 (3-propenyloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., which is a silane coupling agent, was used as the adhesion promoter. <Coatability improver> As the coatability improver, MEGAFAC F-554 (fluorine-containing, lipophilic group-containing oligomer, nonionic surfactant) manufactured by DIC Corporation as a surfactant was used.

<Example 1> (Preparation of black resist 1) Using the coated carbon black ink 1 prepared in the above <Preparation of coated carbon black ink 1>, each component was added so that it might become the ratio shown in Table 1, and it stirred by The device was stirred to dissolve it, and a black resist 1 was prepared. The total solid content of the black resist 1 was 14% by mass.

[Table 1]

In addition, the meaning of the abbreviation of the solvent in Table 1 is as follows. PGMEA: propylene glycol monomethyl ether acetate. MBA: 3-methoxybutyl acetate.

<Example 2> (Preparation of black resist 2) Except for black resist 1, the content ratio of carbon black in all solid components was reduced to 40% by mass, and changed to a value described in Table 2. Except for the content ratios of the other components in the entire solid content component, the black resist 2 having a total solid content content ratio of 14% by mass was prepared in the same manner as the black resist 1.

<Example 3> (Preparation of black resist 3) Except for black resist 1, the content ratio of the photopolymerization initiator in the total solid content was reduced to 3.0% by mass so as to be the value described in Table 2. Except changing the content ratios of the other components in all the solid components, the black resist 3 having a total solid component content ratio of 14% by mass was prepared in the same manner as the black resist 1.

〈Example 4〉 (Preparation of black resist 4) Except that the coated carbon black ink 2 was used instead of the coated carbon black ink 1 in the black resist 1, the content of all solid matter components was changed so as to have the values described in Table 2. Except for the content ratios of other components, in the same manner as for the black resist 1, a black resist 4 having a total solid content content of 14% by mass was prepared.

<Comparative example 1> (Preparation of black resist 5) The same method as black resist 1 was used except that the photopolymerization initiator (1) was changed to the photopolymerization initiator (2) in the black resist 1. A black resist 5 having a total solid content content of 14% by mass was prepared.

<Comparative example 2> (Preparation of black resist 6) The same method as black resist 1 was used except that the photopolymerization initiator (1) was changed to the photopolymerization initiator (3) in black resist 1. A black resist 6 having a total solid content content of 14% by mass was prepared.

<Comparative Example 3> (Preparation of black resist 7) Except that carbon black ink 3 was used instead of coated carbon black ink 1 in black resist 1, and all other solid components were changed so as to have the values shown in Table 2. Except for the content ratio of the components, the black resist 7 having a content ratio of 14% by mass of all solid components was prepared in the same manner as the black resist 1.

<Comparative Example 4> (Preparation of black resist 8) The same method as black resist 7 was used except that the photopolymerization initiator (1) was changed to the photopolymerization initiator (3) in the black resist 7. A black resist 8 having a total solid content content of 14% by mass was prepared.

[Table 2]

(Evaluation of photosensitive resin composition) (1) Production of black resist cured film The black resists 1 to 8 prepared were coated on a glass substrate by a spin coater, dried under reduced pressure, and then heated on a hot plate at 100 ° C. Dry at 120 ° C for 120 seconds. In addition, the coating conditions were adjusted so that the film thickness after coating and drying might become about 1.2 micrometers, respectively. Next, using the exposure machine (EXC-2829-F-00, manufactured by ORC Manufacturing Co., Ltd.), a high-pressure mercury lamp (ADH-3000M-FN, manufactured by ORC Manufacturing Corporation, without optical filter) was used for the obtained dry coating film at 40 mJ / cm ² for full exposure under an unexposed mask. Thereafter, at room temperature (23 ° C), a KOH aqueous solution adjusted to 0.04% by mass with ultrapure water was used as an alkaline developer, and spray development was performed at 2.0 times the dissolution time (spray pressure: 0.1 MPa). Further, spray cleaning was performed with ultrapure water (spray pressure: 0.1 MPa) to obtain a black resist film. Thereafter, it was heat-hardened in an oven at 230 ° C. for 30 minutes to produce a black resist cured film having a film thickness of 1.0 μm. In addition, the so-called dissolution time refers to the time during which the photosensitive layer of the unexposed portion is dissolved during the development process and the surface of the substrate starts to appear. The dissolution time of each black resist is between 30 and 50 seconds. The thickness of the black resist cured film was measured by cutting a part of the film with a cutter to provide a stepped portion, and then measured by a step measurement device Alpha-Step-500 (manufactured by KLA-Tencor). The film thickness can be adjusted by changing the number of revolutions of the spin coater.

(2) Production of black matrix (BM) hardened film For the dry coating film obtained in the same order as in (1) above, an exposure machine (EXC-2829-F-00 manufactured by ORC Manufacturing Co., Ltd.) was used, and a high-pressure mercury lamp (ADH-3000M-FN manufactured by ORC Manufacturing Co., Ltd. without optical filter) Pattern exposure was performed at 40 mJ / cm ² through an exposure mask having a linear opening with a width of 20 μm (close gap 180 μm). Thereafter, at room temperature (23 ° C), a KOH aqueous solution adjusted to 0.04% by mass with ultrapure water was used as an alkaline developer, and spray development was performed at 1.8 times the dissolution time (spray pressure: 0.1 MPa) Furthermore, spray cleaning was performed with ultrapure water (spray pressure: 0.1 MPa) to obtain a BM film. Thereafter, it was heat-hardened in an oven at 230 ° C. for 30 minutes to produce a BM hardened film having a film thickness of 1.0 μm.

(3) Sensitivity evaluation If the exposure sensitivity of the black resist is increased, the line width of the formed BM fine lines tends to increase. The sensitivity of the BM thin line of the BM hardened film was measured by an optical microscope. The measurement results are shown in Table 3.

(4) OD measurement The light-shielding property (optical density, OD) of the black resist cured film was measured by a transmission concentration measuring device GretagMacbeth D200-II (manufactured by GretagMacbeth). The OD was divided by the film thickness to obtain the OD (unit OD) per 1 μm of the film thickness. The measurement results are shown in Table 3.

(5) Measurement of volume resistivity The black resists 1 to 8 prepared were coated on a chrome-plated (Cr) glass substrate with a spin coater, dried under reduced pressure, and then dried on a hot plate at 100 ° C. for 120 seconds. In addition, the coating conditions were adjusted so that the film thickness after heat hardening might become 3.0 micrometers, respectively. Next, using the exposure machine (EXC-2829-F-00, manufactured by ORC Manufacturing Co., Ltd.), a high-pressure mercury lamp (ADH-3000M-FN, manufactured by ORC Manufacturing Corporation, without optical filter) was used for the obtained dry coating film at 40 mJ / cm ² for full exposure under an unexposed mask. Thereafter, it was heat-cured in an oven at 230 ° C. for 180 minutes to produce a black resist cured film having a film thickness of 3.0 μm. A chrome-plated film of this sample was used as a main electrode, and a gold (Au) film formed on a black resist hardened film by evaporation was used as a counter electrode, and an ultra-high-resistance galvanometer (R8340A manufactured by Advantest) was used for measurement. The current value at the applied voltage (DC) of 1 V and 10 V was used to obtain the volume resistivity. The measurement results are shown in Table 3.

[table 3]

From Table 3, the following is known. Unit OD: Examples 1, 3 to 4 having the same content ratio of carbon black, and Comparative Examples 1 to 4 show the same OD value. Therefore, it can be seen that there is no difference in the residual film rate after heat curing for each cured film. Sensitivity: It is also known from Comparative Example 1 that the line width of the 20 μm pattern in Example 1 is wider than 1 μm, and the sensitivity is good. Moreover, in Comparative Example 2, the line width of the 20 μm pattern was as thin as 11 μm, and it was confirmed that a large sensitivity decreased.

Volume resistivity: Comparative Example 1 shows a higher resistance value of more than 13 to the power of 10 at a measurement voltage of 1 V, but a large two-digit decrease at a measurement voltage of 10 V. Furthermore, in Comparative Example 2, a higher resistance value of more than 15 to the power of 10 was displayed at a measurement voltage of 1 V, but a larger decrease was measured at a measurement voltage of 10 V to be reduced to more than 10 to the power of 10. On the other hand, in Example 1, the 15th power is 10 at a measurement voltage of 1 V, and compared with Comparative Example 1, the resistance is higher by two digits. Furthermore, the decrease in resistance at a measurement voltage of 10 V also became small, maintaining a high resistance of more than 10 to 14 power. In addition, compared to Example 1, Example 2 was a person who reduced the amount of coated carbon black, and Example 3 was a person who decreased the amount of photopolymerization initiator, but all maintained high resistance. As is clear from Example 4, the high resistance was maintained even when the high-resistance carbon black whose coating process was changed was used. On the other hand, in Comparative Examples 3 and 4 in which high-resistance carbon black was not used, regardless of the type of the photopolymerization initiator, a large decrease in volume resistivity was seen. From the above results, it can be seen that by using the photopolymerization initiator (c1) as a photopolymerization initiator of a high-resistance black resist, a large effect of improving insulation properties can be obtained.

Regarding the effect of the present invention, the detailed mechanism is not clear, but it is considered as follows. In the conventional high-resistance BM, the carbon black exhibiting electrical conductivity is increased in resistance by coating or the like, and then the gap components (dispersant, alkali-soluble resin, photopolymerizable monomer, photopolymerization initiator, etc.) are further increased. ) Surrounds and prevents the contact between the carbon black particles, thereby ensuring a certain degree of insulation. The interstitial component is an organic substance and is considered to have no large electrical conductivity. However, when focusing on the photopolymerization initiator in the interstitial component, the photopolymerization initiator (2) of Comparative Example 1 has a carbazole ring formed by condensing three aromatic rings, and thus there is a large expansion. π orbits. It is considered that the greatly expanded π orbital becomes a conduction path for electrons, thereby connecting carbon black particles to cause jump conduction easily, thereby making it further difficult to increase resistance. Jumping conduction occurs beyond the energy barrier existing between conductive molecules, so it is easy to occur when the measurement voltage is high. In particular, since the resistivity varies greatly depending on the measured voltage, it is considered that jump conduction occurs.

On the other hand, regarding the photopolymerization initiator (3) of Comparative Example 2, the number of condensation of the aromatic ring is 2 or less. This is advantageous for suppressing the jump conduction from the gap component, but it is based on the diphenyl sulfide skeleton. The oxime ester compound (2) having a carbonyl group between (equivalent to R ^c ) and the oxime ester group (equivalent to-(C = NO- (CO) -R ^a )-) has low sensitivity. The decrease in sensitivity (the decrease in the degree of crosslinking during exposure) is related to the increase in the fluidity of the carbon black particles in the subsequent heat-hardening step, and the carbon black particles become prone to agglomeration. The carbon black particles have narrowed the interval due to agglomeration, which is also easy to cause jump conduction, so it is considered to be related to the decrease in resistance at the measured voltage of 10 V.

In contrast, regarding the photopolymerization initiator (1) of Example 1, the benzofuran ring formed by condensing two aromatic rings was the largest aromatic ring, and the extension of the π orbital was small. It is considered that when the size of the aromatic (condensed) ring possessed by the photopolymerization initiator is reduced, it is related to an increase in the number of jumps required for electrical conduction, thereby achieving further high resistance. The oxime ester compound (1), which is a diphenyl sulfide skeleton (corresponding to R ^c ) and an oxime ester group (corresponding to-(C = NO- (CO) -R ^a )-), is sensitive. Higher, it is considered that the flow and aggregation of the carbon black particles in the hardening and baking step can be suppressed, and the resistance drop at the measured voltage of 10 V can be sufficiently suppressed. Furthermore, it is thought that the photopolymerization initiator (1) has a benzofuran ring, so that it interacts with carbon black and is easily adsorbed near the surface of the particles, and can be adsorbed through the gap between the high-resistance-treated molecules of the high-resistance carbon black. On carbon black surface. It is thought that by this, the exposed light is effectively used before being absorbed by the carbon black, and the hardenability inside the film is improved, whereby the flow and aggregation of the carbon black particles are suppressed, and the resistance drop is easily suppressed. From the above, it can be seen that by using the photosensitive resin composition of the present invention, a high-resistance black matrix having excellent light shielding properties and insulation properties can be provided.

The present invention has been described in detail using specific aspects, but it should be understood that various changes and modifications can be made without departing from the spirit and scope of the present invention.

10‧‧‧ transparent support substrate

20‧‧‧ pixels

30‧‧‧ Organic protective layer

40‧‧‧ inorganic oxide film

50‧‧‧ transparent anode

51‧‧‧ Hole injection layer

52‧‧‧ Hole Transmission Layer

53‧‧‧Light-emitting layer

54‧‧‧ Electron injection layer

55‧‧‧ cathode

100‧‧‧Organic EL element

500‧‧‧Organic luminous body

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL (Electro Luminescence) element provided with the color filter of the present invention.

Claims (8)

A photosensitive resin composition characterized by comprising (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, and (d) a colorant, and (c) ) The photopolymerization initiator contains a photopolymerization initiator (c1) represented by the following general formula (1), and the colorant (d) contains a high-resistance carbon black (d1); (In the above formula (1), R ¹ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent; R ² represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent; R ³ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent; R ⁴ represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aromatic ring group which may have a substituent , Hydroxy or nitro, which may be bonded via a divalent linking group; R ⁵ represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and may have a substituent Aromatic ring group, halogen atom, hydroxyl group or nitro group; A represents an oxygen atom or a sulfur atom; m represents an integer of 0 to 4; n represents an integer of 0 to 4; p represents an integer of 0 to 4; The aromatic ring contained in) may contain a condensed ring, but the number of rings contained in the condensed ring is two or less). The photosensitive resin composition according to claim 1, wherein the high-resistance carbon black (d1) contains a coated carbon black. The photosensitive resin composition according to claim 1 or 2, wherein the volume resistivity of the high-resistance carbon black (d1) is 3 Ω · cm or more. The photosensitive resin composition according to any one of claims 1 to 3, wherein the (a) alkali-soluble resin contains an epoxy (meth) acrylate resin having a carboxyl group. The photosensitive resin composition according to any one of claims 1 to 4, wherein the optical density per film thickness is 2.5 or more. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 5. A black matrix containing hardened material as claimed in claim 6. An image display device having a hardened body as claimed in claim 6.