JP7272267B2 - Photosensitive resin composition, cured product, black matrix and image display device - Google Patents

Description

TECHNICAL FIELD 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 excellent insulating 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 a high-resistance black photosensitive resin composition excellent in light-shielding properties and insulating properties, particularly a photosensitive material for a black matrix (hereinafter sometimes abbreviated as "BM"). suitable for flexible resin compositions.
All contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2017-186138 filed with the Japan Patent Office on September 27, 2017, Japan Patent Office on December 14, 2017 All the contents of the specification, claims, drawings and abstract of Japanese Patent Application 2017-239159 filed in , and part or all of the contents disclosed in the documents etc. cited in this specification It is hereby incorporated by reference into the disclosure content of the present specification.

A color filter is usually formed by forming a black matrix on the surface of a transparent substrate such as glass or plastic, and then sequentially forming pixels of three or more different colors such as red, green, and blue in a lattice or stripe pattern. It is formed in a pattern such as a shape or a mosaic shape. The pattern size varies depending on the application of the color filter and each color, but is usually about 5 to 700 μm.

A pigment dispersion method is currently known as a representative method for manufacturing color filters. When a color filter is produced by a pigment dispersion method, first, a photosensitive resin composition containing a black pigment such as carbon black is coated on a transparent substrate, dried, imagewise exposed and developed, and then heated to a high temperature of 200°C or higher. The BM is formed by heat curing by treatment. Pixels are formed by repeating this for each color such as red, green, and blue, and a color filter having BM and pixels is formed.

The BM is generally arranged in a grid, stripe, or mosaic pattern between red, green, and blue pixels, and serves to improve contrast or prevent light leakage by suppressing color mixture between pixels. be. Therefore, BM is required to have a high light shielding property. In addition, since the edges of pixels such as red, green, and blue formed after forming the BM partially overlap with the BM, a step is formed at the overlapping portion due to the influence of the film thickness of the BM. In this overlapping portion, the flatness of the pixels is impaired, and the liquid crystal cell gap becomes non-uniform or the orientation of the liquid crystal is disturbed, resulting in deterioration of the display performance. Therefore, in recent years, there has been a demand to make the BM thinner, and the pigment content in the photosensitive resin composition tends to be higher in order to exhibit sufficient light-shielding properties even when the BM is made thin.

Furthermore, in order to correspond to various display panel systems, it is also required to increase the volume resistance of BM. For example, Japanese Patent Laid-Open No. 2002-200000 describes an improvement effect by applying a high-resistance BM as a countermeasure against display unevenness in a horizontal electric field type liquid crystal display device. In the case of forming a BM on a TFT (thin film transistor) array substrate or forming a light shielding film for the purpose of preventing malfunction of the TFT element due to light, the BM or the light shielding film come into contact with the pixel electrode or the TFT element. Therefore, in order to prevent a short circuit and leakage current, a highly insulating BM and a light shielding film are essential.

In recent years, there has been a trend toward narrow frame designs that can increase the display area of televisions and mobile displays. The wiring route and arrangement of the electric wiring, which was conventionally arranged in the frame area, have been changed, and the arrangement within the display area has also been devised. When the wiring route is changed and the BM and the electric wiring come into direct contact with each other, a BM with high insulation, that is, a high resistance is required.

On the other hand, regarding the driving of the liquid crystal panel, it is necessary to shorten the response time of the liquid crystal panel in order to display fast-moving moving images without afterimages. This response time can be shortened by increasing the voltage applied to the drive circuit to speed up the orientation change of the liquid crystal substance. Therefore, there is a demand for a high-resistance BM that causes less leakage current even when an applied voltage is higher than before.
For this reason, there has been a demand for realizing even higher resistance while maintaining the conventional BM performance. In response to such demands, for example, Patent Document 2 discloses a method using resin-coated carbon black, and Patent Documents 3 and 4 disclose a method using modified carbon black bonded with a specific organic group. is disclosed.

Japanese Patent Laid-Open No. 9-43590 Japanese Patent Application Laid-Open No. 2013-195538 Japanese special table 2008-517330 WO2003/076527

Conventional high-resistance BM, as disclosed in the above-mentioned Patent Documents 2 to 4, has a high resistance (insulating) by surface treatment such as forming an insulating film on the surface of conductive carbon black. However, the contribution of other constituents to the increase in resistance has not been investigated. The high resistance of BM was mainly due to the carbon black surface treatment technology.

When the present inventors examined the photosensitive resin compositions described in Patent Documents 2 to 4, the volume resistivity of BM was on the order of 10 ¹¹ Ω cm (measurement voltage 10 V), indicating a sufficient level of high resistance. It became clear that it was not reduced (in the order of 10 ¹³ Ω·cm or more). In order to further increase the resistance, there is a method of thickening the coating treatment layer on the surface of the carbon black. A trade-off occurs in terms of performance: (ii) a decrease in the amount of carbon black that can be added causes a decrease in OD (light-shielding properties) due to a decrease in resolution and substrate adhesion due to a decrease in the amount of the curing component; For this reason, it has been difficult to further increase the resistance of BM only by increasing the resistance of carbon black itself.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photosensitive resin composition having excellent light shielding properties and insulating properties and high resistance.

The present inventors have made intensive studies on components other than colorants in order to solve the above problems, and found that the above problems can be solved by including a specific photopolymerization initiator in the photosensitive resin composition. . That is, the gist of the present invention resides in the following.

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

(In formula (1) above, R ¹ represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R ² represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R ³ represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R ⁴ represents an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aromatic ring group, a hydroxyl group, or a nitro group; may be bonded via a divalent linking group.
R ⁵ is an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aromatic represents a ring group, a halogen atom, a hydroxyl group, or a 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 formula (1) 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) comprises coated carbon black.
[3] The photosensitive resin composition according to [1] or [2], wherein the high resistance carbon black (d1) has a volume resistivity of 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], which has an optical density of 2.5 or more per 1 μm of film thickness.

[6] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [5].
[7] A black matrix comprising the cured product of [6].
[8] An image display device comprising the cured product of [6].

ADVANTAGE OF THE INVENTION According to this invention, the high resistance photosensitive resin composition excellent in light-shielding property and insulation can be provided.

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.

Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and can be carried out with various modifications within the scope of the gist thereof.
In the present invention, "(meth)acryl" means "acryl and/or methacryl", and the same applies to "(meth)acrylate" and "(meth)acryloyl".

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

[Photosensitive resin composition]
The photosensitive resin composition of the present invention is a photosensitive resin composition containing (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, and (d) a coloring material. , 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) It is characterized by

In formula (1) above, R ¹ represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R ² represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R ³ represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R ⁴ represents an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aromatic ring group, a hydroxyl group, or a nitro group; may be linked via a divalent linking group.
R ⁵ is an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aromatic represents a ring group, a halogen atom, a hydroxyl group, or a 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 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, thiols, and if necessary, an adhesion improver, a coatability improver, a pigment derivative, a development improver, an ultraviolet absorber, Compounding components such as antioxidants may be included, and each compounding component is usually used in a state of being dissolved or dispersed in an organic solvent.
One of the features of the present invention is that the photopolymerization initiator (c) contains the photopolymerization initiator (c1) in the photosensitive resin composition. First, (c) the photopolymerization initiator will be described.

<(c) Photoinitiator>
The (c) photopolymerization initiator in the present invention contains a photopolymerization initiator (c1) represented by general formula (1) described below.

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

In formula (1) above, R ¹ represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R ² represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R ³ represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R ⁴ represents an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aromatic ring group, a hydroxyl group, or a nitro group; may be bonded via a divalent linking group.
R ⁵ is an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aromatic represents a ring group, a halogen atom, a hydroxyl group, or a 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 formula (1) may contain a condensed ring, but the number of rings contained in the condensed ring is two or less.

Thus, in the photopolymerization initiator (c1) represented by the general formula (1), the aromatic ring contained in the formula (1) may contain a condensed ring. Since the number of rings formed is two or less, that is, two rings or less, the hopping conduction or the like originating from the photopolymerization initiator is suppressed, and it is considered that the insulation becomes good even when the applied voltage is increased.
In addition, since it has a benzofuran ring or a benzothiophene ring, it interacts with carbon black and is easily adsorbed near the particle surface, and is adsorbed on the carbon black surface by slipping through the gaps between the high-resistance treated molecules of the high-resistance carbon black. it is conceivable that. As a result, the exposure light is effectively used before it is absorbed by the carbon black, and the curability inside the film is enhanced, thereby suppressing the flow and aggregation of the carbon black particles, which makes it easier to suppress the decrease in resistance.

( ^R1 )
In formula (1), R ¹ represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
The alkyl group for R ¹ may be linear, branched, cyclic, or a combination thereof. Although the number of carbon atoms in the alkyl group is not particularly limited, it is usually 1 or more, preferably 12 or less, more preferably 6 or less, still more preferably 3 or less, and particularly preferably 2 or less. By making it below the said upper limit, there exists a tendency for crosslink density to become high.
Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl and cyclohexyl groups. Among these, from the viewpoint of sensitivity, a methyl group, an ethyl group, a propyl group, or a butyl group is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is even more preferred.
Examples of substituents that 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, and I, a hydroxyl group, a nitro group, and the like. A methoxy group or a hydroxyl group is preferred from the viewpoint of solvent solubility. From the viewpoint of sensitivity, it is preferably unsubstituted.

The aromatic ring group for R ¹ includes aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The aromatic ring group for R ¹ may contain a condensed ring, but the number of rings contained in the condensed ring is 2 or less. From the viewpoint of insulation, the aromatic ring group is preferably monocyclic.
The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. Storage stability tends to be improved when the content is equal to or higher than the lower limit, and insulating properties tend to be improved when the content is equal to or lower than the upper limit.

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 aromatic hydrocarbon ring groups include groups having one free valence such as benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring and heptalene ring.
Moreover, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring having two or less rings. Examples of aromatic heterocyclic groups include furan ring, thiophene ring, pyrrole ring, 2H-pyran ring, 4H-thiopyran ring, pyridine ring, 1,3-oxazole ring and isoxazole ring having one free valence. ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,3,5-triazine ring, benzofuran ring, 2-benzofuran ring, benzothiophene ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indolizine ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quinolidine ring, benzo groups such as imidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, phthalazine ring, 1,8-naphthyridine ring, purine ring and pteridine ring;
Among these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having one free valence is preferred, and a benzene ring having one free valence is more preferred.

Examples of substituents that 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 , a hydroxyl group, a nitro group, etc., and from the viewpoint of solvent solubility, a methoxy group or a hydroxyl group is preferable. From the viewpoint of sensitivity, it is preferably unsubstituted.

Among these, from the viewpoint of curability, R ¹ is preferably an optionally substituted alkyl group, more preferably an unsubstituted alkyl group, and even more preferably a methyl group.

( ^R2 )
In formula (1), R ² represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
The alkyl group for R ² may be linear, branched, cyclic, or a combination thereof, but from the viewpoint of solvent solubility, linear or branched is preferred, and branched is more preferred. preferable.
Although the number of carbon atoms in the alkyl group is not particularly limited, it 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 preferably 10 or less, more preferably 8 or less. , more preferably 7 or less, particularly preferably 6 or less. When the content is at least the lower limit, the solvent solubility tends to be improved, and when the content is at the upper limit or less, the sensitivity tends to be high.
Specific examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, cyclopentylmethyl group, A cyclopentylethyl group, a cyclohexylmethyl group, a cyclohexylethyl group and the like can be mentioned. Among these, from the viewpoint of solvent solubility, a hexyl group, an isopropyl group, an isobutyl group, an isopentyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclopentylethyl group, or a cyclohexylmethyl group are preferable, and an isobutyl group, an isopentyl group, and a cyclopentylethyl group. , or a cyclohexylmethyl group, more preferably an isopentyl group.
Examples of substituents that 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 and a hydroxyl group, etc., and from the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms is preferred. From the viewpoint of sensitivity, it is preferably unsubstituted.

The aromatic ring group for R ² includes aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The aromatic ring group for R ² may contain a condensed ring, but the number of rings contained in the condensed ring is 2 or less. From the viewpoint of insulation, the aromatic ring group is preferably monocyclic.
The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. When the content is equal to or higher than the lower limit, the molecule tends to be stable, and when the content is equal to or lower than the upper limit, the insulating property tends to be improved.

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 aromatic hydrocarbon ring groups include groups having one free valence such as benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring and heptalene ring.
Moreover, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring having two or less rings. Examples of aromatic heterocyclic groups include furan ring, thiophene ring, pyrrole ring, 2H-pyran ring, 4H-thiopyran ring, pyridine ring, 1,3-oxazole ring and isoxazole ring having one free valence. ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,3,5-triazine ring, benzofuran ring, 2-benzofuran ring, benzothiophene ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indolizine ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quinolidine ring, benzo groups such as imidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, phthalazine ring, 1,8-naphthyridine ring, purine ring and pteridine ring;
Among these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having one free valence is preferred, and a benzene ring having one free valence is more preferred.

Examples of substituents that 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 , a hydroxyl group, a nitro group, etc., and from the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group is preferable. From the viewpoint of sensitivity, it is preferably unsubstituted.

Among these, from the viewpoint of sensitivity, R ² is preferably an optionally substituted alkyl group, more preferably an unsubstituted alkyl group, and still more preferably an isopentyl group. In another aspect, R ² is more preferably an isopentyl group or a cyclopentylethyl group.

( ^R3 )
In the formula (1), R ³ represents an optionally substituted alkyl group or an optionally substituted aromatic ring group, and when m is an integer of 2 or more, They may be the same or different.
The alkyl group for R ³ may be linear, branched, cyclic, or a combination thereof, but from the viewpoint of solvent solubility, linear or branched is preferred, and branched is more preferred. preferable.
Although the number of carbon atoms in the alkyl group is not particularly limited, it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and particularly preferably 4 or less. is. When the content is at least the lower limit, the solvent solubility tends to be good, and when the content is the upper limit or less, the sensitivity tends to be good.
Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl and cyclohexyl groups. Among these, from the viewpoint of sensitivity, a methyl group, an ethyl group, a propyl group, or an isopropyl group is preferred, an ethyl group or an isopropyl group is more preferred, and an isopropyl group is even more preferred.
Examples of substituents that 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 and a hydroxyl group, etc., and from the viewpoint of solvent solubility, an alkoxy group having 1 to 10 carbon atoms is preferable. From the viewpoint of sensitivity, it is preferably unsubstituted.

The aromatic ring group for R ³ includes aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The aromatic ring group for R ³ may contain a condensed ring, but the number of rings contained in the condensed ring is 2 or less. From the viewpoint of insulation, the aromatic ring group is preferably monocyclic.
The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. When the content is equal to or higher than the lower limit, the molecule tends to be stable, and when the content is equal to or lower than the upper limit, the insulating property tends to be improved.

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 aromatic hydrocarbon ring groups include groups having one free valence such as benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring and heptalene ring.
Moreover, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring having two or less rings. Examples of aromatic heterocyclic groups include furan ring, thiophene ring, pyrrole ring, 2H-pyran ring, 4H-thiopyran ring, pyridine ring, 1,3-oxazole ring and isoxazole ring having one free valence. ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,3,5-triazine ring, benzofuran ring, 2-benzofuran ring, benzothiophene ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indolizine ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quinolidine ring, benzo groups such as imidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, phthalazine ring, 1,8-naphthyridine ring, purine ring and pteridine ring;
Among these, from the viewpoint of sensitivity, a phenyl group or a thienyl group is preferable, and a phenyl group is more preferable.

Examples of substituents that 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 , a hydroxyl group, a nitro group, etc., and from the viewpoint of solvent solubility, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is preferable. From the viewpoint of sensitivity, it is preferably unsubstituted.

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

( ^R4 )
In the above formula (1), R ⁴ is an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aromatic ring group, a hydroxyl group, or a nitro group, which may be linked via a divalent linking group, and when n is an integer of 2 or more, they may be the same or different.
In R ⁴ , “these may be bonded via a divalent linking group” means that R ⁴ is bonded to the benzene ring of the formula (1) via a divalent linking group. It means that you may

The alkyl group for R ⁴ may be linear, branched, cyclic, or a combination thereof, but from the viewpoint of solvent solubility, linear or branched is preferred, and branched is more preferred. preferable.
Although the number of carbon atoms in the alkyl group is not particularly limited, it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and particularly preferably 4 or less. is. Solubility tends to be improved by setting the lower limit or more, and sensitivity tends to be improved by setting it to the upper limit or less.
Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl and cyclohexyl groups. Among these, from the viewpoint of sensitivity, a methyl group, an ethyl group, a propyl group, or an isopropyl group is preferred, an ethyl group or an isopropyl group is more preferred, and an isopropyl group is even more preferred.
Examples of substituents that 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 and a hydroxyl group, etc., and from the viewpoint of solvent solubility, an alkoxy group having 1 to 10 carbon atoms is preferred. From the viewpoint of sensitivity, it is preferably unsubstituted.

The alkoxy group for R ⁴ may be linear or branched, but linear is preferred from the viewpoint of sensitivity.
Although the number of carbon atoms in the alkoxy group is not particularly limited, it is usually 1 or more, preferably 2 or more, preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and particularly preferably 4 or less. When the content is at least the lower limit, the solvent solubility tends to be good, and when the content is the upper limit or less, the sensitivity tends to be good.
Specific examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, isopentyloxy, cyclopentyloxy, A hexyloxy group, an isohexyloxy group, a cyclohexyloxy group and the like can be mentioned. Among these, from the viewpoint of sensitivity, a methoxy group, an ethoxy group, or a propoxy group is preferred, a methoxy group or an ethoxy group is more preferred, and an ethoxy group is even more preferred.
Examples of substituents that 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, I and a hydroxyl group, and a hydroxyl group is preferred from the viewpoint of solvent solubility. From the viewpoint of sensitivity, it is preferably unsubstituted.

The aromatic ring group for R ⁴ includes aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The aromatic ring group for R ⁴ may contain a condensed ring, but the number of rings contained in the condensed ring is 2 or less, preferably 2 from the viewpoint of sensitivity. From the viewpoint of insulation, the aromatic ring group is preferably monocyclic.
The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. When the content is equal to or higher than the lower limit, the molecule tends to be stable, and when the content is equal to or lower than the upper limit, the insulating property tends to be improved.

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 aromatic hydrocarbon ring groups include groups having one free valence such as benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring and heptalene ring.
Moreover, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring having two or less rings. Examples of aromatic heterocyclic groups include furan ring, thiophene ring, pyrrole ring, 2H-pyran ring, 4H-thiopyran ring, pyridine ring, 1,3-oxazole ring and isoxazole ring having one free valence. ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,3,5-triazine ring, benzofuran ring, 2-benzofuran ring, benzothiophene ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indolizine ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quinolidine ring, benzo groups such as imidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, phthalazine ring, 1,8-naphthyridine ring, purine ring and pteridine ring;
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 valence is preferred, and a benzofuran ring having one free valence is more preferred.

Examples of substituents that 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. tricyclic groups, halogen atoms such as F, Cl, Br, and I, hydroxyl groups, nitro groups, etc., and from the viewpoint of solvent solubility, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. preferable. From the viewpoint of sensitivity, it is preferably unsubstituted.

Examples of the divalent linking group for bonding via a divalent linking group include -CH ₂ -, -(CH ₂ ) ₂ -, -NH-, -NHCO-, -CO-, -CS-, -COO-, -O-, -S-, etc., among these, -CO-, -NH-, and -O- are preferred from the viewpoint of sensitivity, and -CO- is more preferred.

R ⁴ is for adjusting solubility and light absorption, but from ^the viewpoint of sensitivity and insulation, a benzene ring or a divalent a naphthalene ring linked via a divalent linking group, a thiophene ring linked via a divalent linking group, a benzofuran ring linked via a divalent linking group, or a benzothiophene ring linked via a divalent linking group preferable. The divalent linking group is more preferably -CO-, more preferably a benzofuran ring linked via -CO-.

( ^R5 )
In the above formula (1), R ⁵ is an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted represents an aromatic ring group, a halogen atom, a hydroxyl group, or a nitro group that may be substituted, and when p is an integer of 2 or more, they may be the same or different.

The alkyl group for R ⁵ may be linear, branched, cyclic, or a combination thereof, but from the viewpoint of solvent solubility, linear or branched is preferred, and branched is more preferred. preferable.
Although the number of carbon atoms in the alkyl group is not particularly limited, it is usually 1 or more, preferably 2 or more, preferably 6 or less, more preferably 5 or less, still more preferably 4 or less, and particularly preferably 3 or less. When the content is at least the lower limit, the solvent solubility tends to be good, and when the content is the upper limit or less, the sensitivity tends to be good.
Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl and cyclohexyl groups. Among these, from the viewpoint of sensitivity, a methyl group, an ethyl group, a propyl group, or an isopropyl group is preferred, a methyl group or an ethyl group is more preferred, and an ethyl group is even more preferred.
Examples of substituents that 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 and a hydroxyl group, etc., and from the viewpoint of solvent solubility, an alkoxy group having 1 to 10 carbon atoms is preferable. From the viewpoint of sensitivity, it is preferably unsubstituted.

The alkoxy group for R ⁵ may be linear or branched, but linear is preferred from the viewpoint of sensitivity.
Although the number of carbon atoms in the alkoxy group is not particularly limited, it is usually 1 or more, preferably 2 or more, preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and particularly preferably 4 or less. When the content is at least the lower limit, the solvent solubility tends to be good, and when the content is the upper limit or less, the sensitivity tends to be good.
Specific examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, isopentyloxy, cyclopentyloxy, A hexyloxy group, an isohexyloxy group, a cyclohexyloxy group and the like can be mentioned. Among these, from the viewpoint of sensitivity, a methoxy group, an ethoxy group, or a propoxy group is preferred, a methoxy group or an ethoxy group is more preferred, and an ethoxy group is even more preferred.
Examples of substituents that 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, I and a hydroxyl group, and a hydroxyl group is preferred from the viewpoint of solvent solubility. From the viewpoint of sensitivity, it is preferably unsubstituted.

The alkylthio group for R ⁵ may be linear or branched, but linear is preferred from the viewpoint of sensitivity.
Although the number of carbon atoms in the alkylthio group is not particularly limited, it is usually 1 or more, preferably 2 or more, preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and particularly preferably 4 or less. When the content is at least the lower limit, the solvent solubility tends to be good, and when the content is the upper limit or less, the sensitivity tends to be good.
Specific examples of alkylthio groups include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, tert-butylthio, pentylthio, isopentylthio, cyclopentylthio, hexylthio, and isohexyl. thio group, cyclohexylthio group and the like. Among these, from the viewpoint of sensitivity, a methylthio group, an ethylthio group, or a propylthio group is preferred, a methylthio group or an ethylthio group is more preferred, and an ethylthio group is even more preferred.
Examples of substituents that 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, I and a hydroxyl group, and a hydroxyl group is preferred from the viewpoint of solvent solubility. From the viewpoint of sensitivity, it is preferably unsubstituted.

The aromatic ring group for R ⁵ includes aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The aromatic ring group for R ⁵ may contain a condensed ring, but the number of rings contained in the condensed ring is 2 or less. From the viewpoint of insulation, the aromatic ring group is preferably monocyclic.
The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. When the content is equal to or higher than the lower limit, the molecule tends to be stable, and when the content is equal to or lower than the upper limit, the insulating property tends to be improved.

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 aromatic hydrocarbon ring groups include groups having one free valence such as benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring and heptalene ring.
Moreover, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring having two or less rings. Examples of aromatic heterocyclic groups include furan ring, thiophene ring, pyrrole ring, 2H-pyran ring, 4H-thiopyran ring, pyridine ring, 1,3-oxazole ring and isoxazole ring having one free valence. ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,3,5-triazine ring, benzofuran ring, 2-benzofuran ring, benzothiophene ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indolizine ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quinolidine ring, benzo groups such as imidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, phthalazine ring, 1,8-naphthyridine ring, purine ring and pteridine ring;
Among these, from the viewpoint of sensitivity, a phenyl group or a thienyl group is preferable, and a phenyl group is more preferable.

Examples of substituents that 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 , a hydroxyl group, a nitro group, etc., and from the viewpoint of solvent solubility, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is preferable. From the viewpoint of sensitivity, it is preferably unsubstituted.

Halogen atoms for R ⁵ include F, Cl, Br, I and the like.

Among these, from the viewpoint of sensitivity, R ⁵ is preferably a methyl group, a methoxy group, a phenyl group or a thienyl group, more preferably a methoxy group.

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

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

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

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

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

In addition, in the above formula, C ₃ H ₇ represents an isopropyl group.

<Other Photoinitiators (c2)>
The (c) photopolymerization initiator in the present invention is, in addition to the photopolymerization initiator (c1), other photopolymerization initiators ( c2) may be contained.
Other photopolymerization initiators (c2) include, for example, metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; Hexaarylbiimidazole derivatives described in JP-A-2000-56118; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in JP-A-10-39503; Radical activators such as aryl-α-amino acids, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; Japanese Patent Application Laid-Open No. 2000-80068, Japan Examples thereof include oxime ester derivatives described in Japanese Patent Application Laid-Open No. 2006-36750.

Specifically, for example, metallocene compounds include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl ), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl), dicyclopentadienyl titanium di( 2,6-difluorophenyl), dicyclopentadienyl titanium di(2,4-difluorophenyl), di(methylcyclopentadienyl) titanium bis(2,3,4,5,6-pentafluorophenyl), di(methylcyclopentadienyl) titanium bis(2,6-difluorophenyl), dicyclopentadienyl titanium [2,6-di-fluoro-3-(pyrrolyl)-phenyl] and the like.

Further, 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.

Further, halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'- benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2′-(6″-benzofuryl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

Further, halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazine and the like.

Further, α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- morpholinophenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate -, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4 -diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone and the like.

As other photopolymerization initiators, oxime ester derivatives are particularly effective in terms of sensitivity. oxime ester derivatives are useful, and oxime ester compounds (1) represented by the following general formula (c2-1) and oxime ester compounds (2) represented by the following general formula (c2-2) are mentioned. Among the oxime ester derivatives, the oxime ester compound (1) is particularly preferred from the viewpoint of sensitivity and adhesion to substrates.
Oxime ester derivatives have a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals, so they are highly sensitive in small amounts and stable against thermal reactions. It is possible to design a photosensitive resin composition with a small amount and high sensitivity. In particular, from the viewpoint of light absorption for the i-line (365 nm) of the exposure light source, the oxime ester compound (1) containing an optionally substituted carbazolyl group (a group having an optionally substituted carbazole ring) In this case, this structural characteristic is well expressed and is more preferable. At present, there is a demand in the market for a thin BM (black matrix) having a high degree of light shielding, and the pigment concentration is becoming higher and higher.

In formulas (c2-1) and (c2-2), R ^a to R ^c are each independently an optionally substituted alkyl group or an optionally substituted aromatic ring group represents

Commercially available products of such oxime ester compound (1) include OXE-02 manufactured by BASF Corp., TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Power Electronics Co., Ltd., and the like.

Specific examples of suitable oxime ester compounds include the compounds exemplified below, but are by no means limited to these compounds.

In addition, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone, 1-hydroxy -1-(p-dodecylphenyl)ketone, 2-methyl-(4′-methylthiophenyl)-2-morpholino-1-propanone, acetophenone such as 1,1,1-trichloromethyl-(p-butylphenyl)ketone Derivatives; Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone; p-dimethylamino Benzoic acid ester derivatives such as ethyl benzoate and ethyl p-diethylaminobenzoate; acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine; phenazine derivatives such as 9,10-dimethylbenzphenazine and anthrone derivatives such as benzanthrone.

<Sensitizing dye>
If necessary, the photopolymerization initiator can be used in combination with a sensitizing dye corresponding to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. These sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703 and JP-A-5-289335. A coumarin dye having a heterocycle described in the publication, Japanese Patent Laid-Open No. 3-239703, a 3-ketocoumarin compound described in Japanese Patent Laid-Open No. 5-289335, and a Japanese Patent Laid-Open No. 6-19240. pyrromethene dyes, and others, Japanese Patent Laid-Open Publication No. 47-2528, Japanese Patent Laid-Open Publication No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Patent Laid-Open Publication No. 48-84183, Japan JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69 Publications, JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, the dialkylaminobenzene skeleton described in JP-A-4-288818 and the like can be exemplified.

Preferred among these sensitizing dyes are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone , benzophenone compounds such as 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5 ] benzoxazole, 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-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)- 1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine , p-dialkylaminophenyl group-containing compounds such as (p-diethylaminophenyl)pyrimidine.
Among these, the most preferred is 4,4'-dialkylaminobenzophenone.
The sensitizing dyes may be used singly or in combination of two or more.

(c) The content of the photopolymerization initiator is not particularly limited, but usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more in the total solid content of the photosensitive resin composition of the present invention. is usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 8% by mass or less, and particularly preferably 5% by mass or less. . When it is at least the above lower limit, it tends to be possible to suppress a decrease in sensitivity, and when it is at most the above upper limit, it tends to be possible to improve the solubility of unexposed portions in a developer. 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, even more preferably 3 to 10% by mass, and 3 to 8% by mass. More preferably, 3 to 5% by mass is even more preferable.

Although the content of the photopolymerization initiator (c1) is not particularly limited, it is usually 0.3% by mass or more, preferably 0.5% by mass or more, or more in the total solid content of the photosensitive resin composition of the present invention. It is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and is usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass. % by mass or less, more preferably 8% by mass or less, particularly preferably 5% by mass or less. By setting it to the lower limit or more, there is a tendency that both sensitivity and insulation tend to be compatible, and by setting it to the above upper limit or less, there is a tendency that the solubility of the unexposed portion in the developer can be improved. . 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, even more preferably 0.5 to 15% by mass, even more preferably 1 to 10% by mass, 2 to 8% by mass is particularly preferred, and 3 to 5% by mass is even more preferred.
(c) The content of the photopolymerization initiator (c1) with respect to the total amount of the photopolymerization initiator is not particularly limited, but is usually 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably It is 80% by mass or more, more preferably 90% by mass or more, particularly preferably 95% by mass or more, and usually 100% by mass or less. Moreover, there exists a tendency for insulation to increase by making it more than the said lower limit. In addition, it is also possible to adjust the resistivity by the content ratio of the photopolymerization initiator (c1) to the total amount of the photopolymerization initiator (c).

Further, when a sensitizing dye is used, its content is not particularly limited. 10% by mass.

<(a) alkali-soluble resin>
The photosensitive resin composition of the present invention contains (a) an alkali-soluble resin. (a) The alkali-soluble resin is particularly limited as long as the solubility of the exposed area and the non-exposed area in alkali development changes after the coating film obtained by coating and drying the photosensitive resin composition is exposed. However, it is preferably an alkali-soluble resin having a carboxyl group. Moreover, those having an ethylenically unsaturated group are preferable, and alkali-soluble resins having an ethylenically unsaturated group and a carboxyl group are more preferable. Specifically, epoxy (meth)acrylate resins and acrylic copolymer resins having a carboxyl group can be mentioned. 1), (A2-2), (A2-3) and (A2-4), and these may be used alone or in combination of two or more. 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 is produced by a reaction of a reaction product of an epoxy resin with an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group. It is a resin obtained by further reacting polybasic acid and/or its anhydride with the hydroxyl groups obtained. Further, before reacting the polybasic acid and/or its anhydride with a hydroxyl group, after reacting a compound having two or more substituents capable of reacting with the hydroxyl group, the polybasic acid and/or its anhydride Resins obtained by reacting are also included in epoxy (meth)acrylate resins. The epoxy (meth)acrylate resin also includes a resin obtained by reacting the carboxyl group of the resin obtained by the above reaction with a compound having a reactive functional group.
Thus, the epoxy (meth)acrylate resin has substantially no epoxy group in terms of its chemical structure, and is not limited to "(meth)acrylate", but is made from an epoxy resin, and Since "(meth)acrylate" is a typical example, the name is used in this way according to common practice.

When making color filters, the unexposed areas are usually dissolved in alkaline developer, so polymer resins with acidic functional groups such as hydroxyl groups, carboxyl groups, phosphoric acid groups, and sulfonic acid groups are used as alkali-soluble resins. be done. Among these, polymer resins having a carboxyl group are preferred from the viewpoint of solubility in an alkaline developer. In addition, although the phosphate group and sulfonic acid group have higher acidity than the carboxyl group, they tend to react with initiators, monomers, dispersants, and other additives having basic groups in the photosensitive resin composition. , storage stability may deteriorate.

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

<Epoxy (meth)acrylate resin (A1-1)>
Examples of epoxy resins used as raw materials include bisphenol A type epoxy resins (e.g., "jER (registered trademark; hereinafter the same) 828", "jER1001", "jER1002", "jER1004" manufactured by Mitsubishi Chemical Corporation, Nippon Kayaku "NER-1302" (epoxy equivalent 323, softening point 76 ° C.) manufactured by Mitsubishi Chemical Corporation, etc.), bisphenol F type resin (for example, Mitsubishi Chemical Corporation "jER807", "jER4004P", "jER4005P", "jER4007P", Japan Kayaku "NER-7406" (epoxy equivalent 350, softening point 66 ° C.), etc.), bisphenol S type epoxy resin, biphenyl glycidyl ether (e.g. Mitsubishi Chemical "jERYX-4000"), phenol novolak type Epoxy resin (e.g., Nippon Kayaku Co., Ltd. "EPPN (registered trademark) -201", Mitsubishi Chemical Co., Ltd. "jER-152", "jER-154", Dow Chemical Co., Ltd. "DEN- 438”), (o, m, p-) cresol novolak type epoxy resin (for example, Nippon Kayaku Co., Ltd. “EOCN (registered trademark; the same shall apply hereinafter)-102S”, “EOCN-1020”, “EOCN-104S ”), triglycidyl isocyanurate (e.g., “TEPIC (registered trademark)” manufactured by Nissan Chemical Industries, Ltd.), trisphenolmethane type epoxy resin (e.g., “EPPN-501”, “EPPN-502” manufactured by Nippon Kayaku Co., Ltd. , “EPPN-503”), alicyclic epoxy resin (“Celoxide (registered trademark) 2021P”, “Celoxide EHPE” manufactured by Daicel), glycidylation of phenolic resin by reaction of dicyclopentadiene and phenol Epoxy resins (for example, "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resins represented by the following general formulas (a1) to (a5), etc. are preferably can be used. Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as the epoxy resin represented by the following general formula (a1), and "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as the epoxy resin represented by the following general formula (a2) NC-3000", and "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (a4).

In the above 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. A plurality of R ¹¹ present in one molecule may be the same or different.

In the general formula (a2), b12 is an average value and represents a number from 0 to 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, a phenyl group, a naphthyl group or a biphenyl group. Plural R ²¹ in one molecule may be the same or different.

In general formula (a3) above, X represents a linking group represented by general formula (a3-1) or (a3-2) below. However, it contains one or more adamantane structures in its molecular structure. b13 represents an integer of 2 or 3;

In the above general formulas (a3-1) and (a3-2), R ³¹ to R ³⁴ and R ³⁵ to R ³⁷ are each independently an optionally substituted adamantyl group, a hydrogen atom, a substituent or an optionally substituted phenyl group. Moreover, * in the formula represents a binding site in the general formula (a3).

In the above general formula (a4), p and q each independently represents an integer of 0-4. R ⁴¹ and R ⁴² each independently represent an alkyl group having 1 to 20 carbon atoms or a halogen atom. 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.

In general formula (a5) above, each of R ⁵¹ to R ⁵⁴ independently represents 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. show. 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. Each R ⁵⁶ 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, epoxy resins represented by any one of general formulas (a1) to (a5) are preferably used.

α,β-unsaturated monocarboxylic acids and/or α,β-unsaturated monocarboxylic acid esters having a carboxyl group include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyladipic acid, 2 - (meth) acryloyloxyethyl phthalate, 2-(meth) acryloyloxyethyl hexahydrophthalate, 2-(meth) acryloyloxyethyl maleate, 2-(meth) acryloyloxypropyl succinate, 2 - (meth) acryloyloxypropyl adipate, 2-(meth) acryloyloxypropyl tetrahydrophthalate, 2-(meth) acryloyloxypropyl phthalate, 2-(meth) acryloyloxypropyl maleate, 2- (Meth) acryloyloxybutyl succinate, 2-(meth) acryloyloxybutyl adipate, 2-(meth) acryloyloxybutyl hydrophthalate, 2-(meth) acryloyloxybutyl phthalate, 2-( As meth)acryloyloxybutyl maleate and (meth)acrylic acid esters, lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone and δ-valerolactone are added to (meth)acrylic acid and the terminal A monomer having one hydroxyl group at the end, or a monomer having one hydroxyl group at the end such as hydroxyalkyl (meth) acrylate, or a terminal having one hydroxyl group such as pentaerythritol tri (meth) acrylate Acid (anhydride) such as (anhydride) succinic acid, (anhydride) phthalic acid, (anhydride) maleic acid is added to a compound having a hydroxyl group, and one or more ethylenically unsaturated groups and one carboxyl group at the end are added. (Meth)acrylic acid esters having (Meth)acrylic acid dimers and the like are also included.

Among these, (meth)acrylic acid is particularly preferable from the viewpoint 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 technique can be used. For example, an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group is reacted with an epoxy resin at a temperature of 50 to 150° C. in the presence of an esterification catalyst. be able to. Examples of the esterification catalyst used here include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride. .

The epoxy resin, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used singly or in combination of two. The above may be used in combination.
The amount of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents per equivalent of the epoxy group of the epoxy resin. , more preferably in the range of 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 or more, the introduction amount of the unsaturated group becomes sufficient, and the amount of unsaturated groups continues to increase. Reaction with a basic acid and/or its anhydride becomes sufficient, and there is a tendency that a large amount of epoxy groups can be suppressed from remaining. On the other hand, by setting the amount to be equal to or less than the upper limit, it is possible to suppress the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group from remaining as an unreacted product. Tend.

Polybasic acids and/or their anhydrides include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid. One or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, anhydrides thereof, and the like.

Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof are preferred. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, and biphenyltetracarboxylic dianhydride.

A known method can also be used for the addition reaction of polybasic acids and/or their anhydrides. The desired product can be obtained by continuing the reaction under the same conditions as the addition reaction of the carboxylic acid ester. The amount of polybasic acid and/or its anhydride component added is preferably such that the resulting carboxyl group-containing epoxy (meth)acrylate resin has an acid value in the range of 10 to 150 mgKOH/g. It is preferred to be in the range of ~140 mg KOH/g. Alkali developability tends to be improved by setting the content to the above lower limit or more, and curability tends to be improved by setting the content to be the above upper limit or less.

<Epoxy (meth)acrylate resin (A1-2)>
A polyhydric alcohol such as trimethylolpropane, pentaerythritol, and dipentaerythritol may be added during the addition reaction of the polybasic acid and/or its anhydride for the resin (A1-1) to introduce a multibranched structure. Well, by doing so an epoxy (meth)acrylate resin (A1-2) is obtained.
Epoxy (meth)acrylate resins (A1-1) and (A1-2) are usually an epoxy resin and an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group. After mixing a polybasic acid and / or an anhydride thereof with the reaction product, or an epoxy resin and an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid having a carboxyl group It can be obtained by mixing a polybasic acid and/or its anhydride and a polyhydric alcohol with a reactant with an ester, followed by heating. In this case, the order of mixing the polybasic acid and/or its anhydride and the polyhydric alcohol is not particularly limited. Any present in a mixture of a reaction product of 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 polyhydric alcohol when heated A polybasic acid and/or its anhydride undergoes an addition reaction with the hydroxyl group of .

Epoxy (meth)acrylate resins having a carboxyl group may be used singly or as a mixture of two or more resins.
The amount of polyhydric alcohol used is, from the viewpoint of exhibiting effects while suppressing thickening and gelation, an epoxy resin and an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated having a carboxyl group. It is usually about 0.01 to 0.5 times the weight, preferably about 0.02 to 0.2 times the weight of the reaction product with the monocarboxylic acid ester.

The acid value of the epoxy (meth)acrylate resin having a carboxyl group is usually 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, preferably 150 mgKOH/g. g or less is more preferable. When the content is equal to or higher than the lower limit, the developability tends to be improved, and when the content is equal to or lower than the upper limit, the alkali resistance tends to be improved. A combination of the upper limit and the lower limit is preferably 10 to 200 mgKOH/g, more preferably 50 to 150 mgKOH/g, even more preferably 80 to 150 mgKOH/g.

The polystyrene equivalent weight average molecular weight (Mw) of the epoxy (meth)acrylate resin having a carboxyl group, measured by gel permeation chromatography (GPC), is preferably 1000 or more, more preferably 1500 or more, and more preferably 2000. It is more preferably 5000 or more, and particularly preferably 5000 or more. Also, it is preferably 20,000 or less, more preferably 15,000 or less, even more preferably 10,000 or less, even more preferably 8,000 or less, and particularly preferably 6,000 or less. Sensitivity, coating film strength, and alkali resistance tend to be improved by setting it to the lower limit or more, and developability and resolubility tend to be improved by setting it to the upper limit or less. . The combination of the upper limit and the lower limit is preferably 1000 to 20000, more preferably 1500 to 20000, still more preferably 1500 to 15000, even more preferably 2000 to 15000, even more preferably 2000 to 10000, even more preferably 2000 to 8000. , 2000-6000 are even more preferred.

<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, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open Publication No. 10-300922, Japanese Patent Laid-Open Publication No. 11-140144, Japan Japanese Patent Laid-Open No. 11-174224, Japanese Patent 2000-56118, Japanese Patent 2003-233179, Japanese Patent 2007-270147, etc. Molecular compounds can be used, but the following resins (A2-1) to (A2-4) are preferred, among which resin (A2-1) is particularly preferred.

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

From the viewpoint of sensitivity, the photosensitive resin composition of the present invention includes (A1-1), (A1-2), (A2-1), and (A2-3) as alkali-soluble resins containing an ethylenically unsaturated group. It is further preferable to include at least one of In the photosensitive resin composition of the present invention, from the viewpoint of surface curability, at least (A1-1) and (A1-2), which are epoxy (meth)acrylate resins as alkali-soluble resins containing ethylenically unsaturated groups, It is particularly preferred to include either.

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 may be selected from resins commonly used in photosensitive resin compositions for color filters. Examples thereof include alkali-soluble resins described in JP-A-2007-271727, JP-A-2007-316620, JP-A-2007-334290, and the like.

(a) The content of the alkali-soluble resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more in the total solid content of the photosensitive resin composition of the present invention. It is 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 particularly preferably 20% by mass or less. When it is at least the lower limit, the solubility of the unexposed portion in the developer tends to be good, and when it is at most the upper limit, excessive permeation of the developer into the exposed portion can be suppressed. This tends to improve sharpness and adhesion of images. 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 15 to 20% by mass. Especially preferred.
As described above, the photosensitive resin composition of the present invention includes (a) alkali-soluble resins (A1-1), (A1-2), (A2-1), and (A2-2) described above. , (A2-3) and (A2-4) are preferably included, and when other alkali-soluble resins are included, the content ratio is 20 mass with respect to the total of the alkali-soluble resins (a) % or less, preferably 10 mass % or less.

<(b) Photopolymerizable Monomer>
The photosensitive resin composition of the present invention contains (b) a photopolymerizable monomer from the viewpoint 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"). . Specifically, for example, (meth)acrylic acid, (meth)acrylic acid alkyl ester, acrylonitrile, styrene, and a carboxylic acid having one ethylenically unsaturated bond, a polyhydric or monohydric alcohol monoester, and the like. mentioned.

In the present invention, it is particularly desirable to use polyfunctional ethylenic monomers 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, particularly preferably 6 or more, and usually 10 or less, preferably 8 or less. The sensitivity of the photosensitive resin composition tends to be high when it is at least the above lower limit, and the cure shrinkage during polymerization tends to be small when it is at most the above upper limit. The combination of the upper limit and the lower limit is preferably 2 to 10, more preferably 3 to 10, even more preferably 4 to 8, even more preferably 5 to 8, and even more preferably 6 to 8.
Examples of polyfunctional ethylenic monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic poly Esters obtained by an esterification reaction between a polyhydric hydroxy compound such as a hydroxy compound and an unsaturated carboxylic acid or a polybasic carboxylic acid are included.

Esters of the aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, and methacrylic acid esters obtained by replacing the acrylates of these exemplary compounds with methacrylates Similarly, itaconate instead of itaconate, crotonate instead of clonate, maleate instead of maleate, and the like.

Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. etc.
A polybasic carboxylic acid and an unsaturated carboxylic acid and an ester obtained by an esterification reaction of a polyhydric hydroxy compound are not necessarily single substances, but typical examples include acrylic acid, phthalic acid, and Examples include condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

Other examples of polyfunctional ethylenic monomers used in the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound, a polyol and a hydroxyl group-containing (meth)acrylic acid ester. Urethane (meth)acrylates such as those obtained; epoxy acrylates such as addition reaction products of polyepoxy compounds and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate and vinyl group-containing compounds such as divinyl phthalate are useful.
These may be used individually by 1 type, and may use 2 or more types together.

(b) The content of the photopolymerizable monomer is usually 1% by mass or more, preferably 5% by mass or more, and usually 90% by mass or less, preferably 70% by mass, based on the total solid content of the photosensitive resin composition. % by mass or less, more preferably 50% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less. By setting the content of the photopolymerizable monomer to the above lower limit or more, there is a tendency that photocuring by ultraviolet irradiation is improved and alkali developability is also improved. When the value is equal to or less than the above upper limit, there is a tendency that the permeability of the developing solution to the exposed area becomes appropriate, and good images 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 5 to 20% by mass. More preferably, 5 to 10% by mass is even more preferable.

<(d) Colorant>
The photosensitive resin composition of the present invention contains (d) a coloring material. (d) By containing a coloring material, it is possible to form a colored pattern such as a black matrix or a colored spacer. A coloring material refers to a material that colors the photosensitive resin composition of the present invention.

The (d) coloring material 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 it is carbon black treated to have a high resistance. Examples of the high resistance treatment include surface coating treatment with resin (Japanese Patent Laid-Open No. 2002-249678, Japanese Patent Laid-Open No. 2016-65992), surface coating treatment with dye (International Publication No. 2013/129555). , surface oxidation treatment (Japanese Patent No. 4464081) or surface modification treatment with an organic group having an ionic group (Japanese Patent Publication No. 2008-517330).

More specifically, in the method of coating a surface with a resin described in Japanese Patent Application Laid-Open No. 2002-249678, carbon black is subjected to a graft reaction to bond a functional group to the surface of the carbon black, which is then treated with a resin. By doing so, the surface of the carbon black is coated with a resin. Here, the compound used for the graft reaction treatment of carbon black is a compound capable of reacting with the polymerization-inhibiting functional group, for example, a photopolymerizable compound having an ethylenically unsaturated double bond and other functional groups. is mentioned. Functional groups other than ethylenically unsaturated double bonds include, for example, epoxy group, thioepoxy group, aziridine group, oxazoline, N-hydroxyalkylamide group, isocyanate group, amino group and the like. Examples include glycidyl (meth)acrylate, allyl glycidyl ether, 2,3-epithiopropyl (meth)acrylate, N-(meth)acryloylaziridine, 2-(1-aziridinyl)ethyl (meth)acrylate, 2-iso propenyl-2-oxazoline, N-hydroxyethyl (meth)acrylamide, isocyanatoethyl (meth)acrylate, allylamine and the like. Epoxy-based resins, particularly polyfunctional epoxy resins, are preferred as resins for coating carbon black. Specific examples of polyfunctional epoxy resins include glycidylamine epoxy resins, triphenylglycidylmethane epoxy resins, tetraphenylglycidylmethane epoxy resins, aminophenol epoxy resins, diaminodiphenylmethane epoxy resins, phenol novolak epoxy resins, Ortho-cresol type epoxy resins, bisphenol A novolac type epoxy resins, and the like.

In the method of surface coating with a dye described in WO 2013/129555, first, carbon black as a raw material is mixed with water to form a slurry, heated and stirred for a predetermined time to wash the carbon black, cooled and then washed with water again. Next, water is added to the obtained carbon black to form a slurry again, an oxidizing agent is added, and the slurry is stirred at a predetermined temperature for a predetermined time to oxidize the surface of the carbon black, followed by washing with water. The oxidation treatment is performed several times by changing the type of oxidizing agent, if necessary. Next, the resulting oxidized carbon black is mixed with water to form a slurry again, and the dye is added to the desired dye-coated carbon black so that the predetermined content is as described above. Stir for a period of time to adsorb and coat the dye on the surface of the carbon black. Further, an equimolar amount of metal or metal salt is added to the added dye, and the mixture is stirred at 30 to 70° C. for 1 to 5 hours to form a lake of the dye with the metal or metal salt to fix the dye on the surface of the carbon black. After cooling, this is washed with water, filtered and dried to obtain the desired dye-coated carbon black.
The dye used for dye-coated carbon black is not particularly limited as long as it can be adsorbed on the surface of carbon black, and known basic dyes, acid dyes, direct dyes, reactive dyes, etc. are used. However, since the sulfone group and carboxyl group interact with the functional group on the carbon black, the amino group and the alkali-soluble resin react, and it can be insolubilized with aluminum sulfate, etc., Nonionic dyes are more suitable for use. Further, in order to make the resulting black matrix more highly light-shielding, it is preferable to use a dye of a dark color close to black having high light absorption. Specific examples of such dyes include Food Black No. 1, Food Black No. 2, Food Red No. 40, Food Blue No. 1, Food Yellow No. 7, Bernacid Red 2BMN, 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) (manufactured by BASF), Basacid Blue 750 (manufactured by BASF), Bernacid Red (Bemcolors, Poughkeepsie, N.Y.), BASF Basacid Black SE 0228 (manufactured by BASF) and other acid dyes of various colors, Pontamine (registered trademark) Brilliant Bond Blue A and other Pontamine Brilliant Bond Blue A and other Pontamine dyes (Ba Yer Chemicals Corporation, Pittsburgh, PA), Cartasol® Yellow GTF Presscake (Sandoz, Inc.); Cartasol Yellow GTF Liquid Special 110 (Sandoz, Inc.); Yellow Shade 1 6948 (manufactured by Tricon), Direct Brilliant Pink B (manufactured by Crompton & Knowles), Carta (registered trademark) Black 2GT (manufactured by Sandoz, Inc.), Sirius (registered trademark) Supra Yellow GD 167, Cartasol Brilliant Yellow 4GF (manufactured by Sandoz); Registration Trademarks) Yellow CGP (manufactured by Ciba-Geigy), Pyrazol Black BG (manufactured by JCI), Diazol Black RN Quad (manufactured by JCJ), Pontamine Brilliant Bond Blue; Y. 34, Cibacron Brilliant Red 3B-A (Reactive Red 4) (manufactured by Aldrich Chemical, Milwaukee, WI), Dimarene Brilliant Red X-2B (Reactive Red 56) (Pylam Prod. Ucts, Inc. Tempe, AZ company), Levafix® Brilliant Red E-4B, Levafix Brilliant Red F-6BA, and similar Levafix dyes Dystar L. P. (Charlotte, NC), Procion® Red H8B (Reactive Red 31) (JCI America), various reactive dyes such as Neozapon® Red 492 (BASF) , Orasol (registered trademark) Red G (manufactured by Ciba-Geigy), Aizen (registered trademark) Spilon (registered trademark) RedC-BH (manufactured by Hodogaya Chemical Company), Spirit Fast Yellow 3G, Aizen Spilon Yellow C-GNH (Hodo gaya Chemical Company), Orasol Black RL (Ciba-Geigy), Orasol Black RLP (Ciba-Geigy), Savinyl Black RLS (Sandoz), Orasol Blue GN (Ciba-Geigy company), Luxol Blue MBSN (manufactured by Morton-Thiokol) and Morfast (registered trademark) Black Concentrate A (manufactured by Morton-Thiokol). These may be used alone or in combination of two or more.

In the method of surface oxidation treatment described in Japanese Patent No. 4464081, carbon black is treated with an oxidizing agent in order to efficiently generate functional groups such as carboxyl groups on the surface of carbon black particles. As the oxidizing agent, for example, peroxodiates such as peroxodisulfate, peroxodiborate, peroxodicarbonate and peroxodiphosphate are preferably used. etc. are preferable.

In the method described in Japanese Patent Publication No. 2008-517330, the surface is modified with an organic group having an ionic group. Here, the organic group includes, for example, an arylene group, a heteroarylene group or an alkylene group, and the ionic group includes, for example, a carboxylic acid group, a sulfonic acid group, an alkylsulfate group, and an alkylamine group. or an alkylammonium group or a salt thereof.

Thus, examples of high-resistance carbon black include resin-coated carbon black, dye-coated carbon black, oxidation-treated carbon black, and carbon black surface-modified with an organic group having an ionic group. However, from the viewpoint of insulation, coated carbon black is preferred, resin-coated carbon black and dye-coated carbon black are more preferred, and resin-coated carbon black is even more preferred. These treatments for increasing the resistance of carbon black may be used in combination.

The carbon atom ratio in the surface composition of the high resistance carbon black is preferably 95% or less, more preferably 90% or less. On the other hand, the carbon atom ratio is usually 70% or more, preferably 80% or more, more preferably 85% or more. By setting the carbon atom ratio in the surface composition of the high resistance carbon black to the above upper limit or less, the effect of the surface treatment is large, the powder resistivity can be easily increased, and the volume resistance of the obtained pattern is the desired value. tend to be easy to On the other hand, by setting the carbon atom ratio in the surface composition of the high-resistance carbon black to the lower limit or more, the light-shielding property tends to be improved. The combination of the upper limit and the lower limit is preferably 70-95%, more preferably 80-95%, even more preferably 85-90%.
The ratio of each atom in the surface composition of high resistance carbon black can be measured by X-ray photoelectron spectroscopy (XPS). More specifically, measurement can be performed using monochromatic AlKα1,2 rays (1486.6 eV) as excitation X-rays, with an X-ray diameter of 1 mm and a photoelectron escape angle of 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, further preferably 5 Ω·cm or more, and 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 40 Ω-cm. The following is more preferable, 30 Ω·cm or less is even more preferable, and 20 Ω·cm or less is particularly preferable. The insulating property tends to be improved by making it equal to or higher than the lower limit.

The volume resistivity of high resistance carbon black (d1) can be measured by adopting the method described in Japanese Patent Application 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 Co., Ltd. can also be used for measurement using a constant current application method.
As a measurement procedure, first, put about 2 g of a sample in a Teflon (registered trademark) container with an inner diameter of 2 cm with a brass electrode attached to the bottom, cover with a Teflon rod with a brass electrode attached to the tip, Tensilon A load is applied at a speed of 0.2 mm/min by , and held at 50 kg/cm ² for 1 minute, then the current is set to 1 mA and the resistance is measured with a high sensitivity tester. Then, the volume resistivity is calculated by the following formula from the bulkiness and resistance value of the powder under this load.

Volume resistivity (Ω cm) =
Cross-sectional area of powder (cm ² ) × resistance value (Ω)/bulk height of powder (cm)

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

The (d) colorant in the photosensitive resin composition of the present invention contains high resistance carbon black (d1), and may further contain other colorant (d2). As other coloring materials, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance, and the like.

Pigments of various colors such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments and black pigments can be used. In addition to organic pigments such as azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments, various inorganic pigments can also be used. is.

Specific examples of pigments that can be used in the present invention are shown below by pigment numbers. In addition, terms such as "C.I. Pigment Red 2" mentioned below mean a color index (C.I.).
As a red pigment, C.I. I. 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 these, C.I. I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, 254 may be mentioned.

As a blue pigment, C.I. I. 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 can be mentioned. Among these, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, more preferably C.I. I. Pigment Blue 15:6 may be mentioned.
As a green pigment, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 can be mentioned. Among these, C.I. I. Pigment Green 7, 36, 58 may be mentioned.

As a yellow pigment, C.I. I. 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 can be mentioned. Among these, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.

As an orange pigment, C.I. I. 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 can be mentioned. Among these, C.I. I. Pigment Orange 38, 71 may be mentioned.

As a purple pigment, C.I. I. 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 can be mentioned. Among these, C.I. I. Pigment Violet 19, 23, more preferably C.I. I. Pigment Violet 23 may be mentioned.

Further, when the photosensitive resin composition of the present invention is used for light-shielding purposes such as a resin black matrix of a color filter, it is preferable to use a black colorant as the other colorant. As for the black colorant, one type of black colorant may be used alone, or red, green, and blue colorants may be mixed and used as a black colorant. These coloring materials can be appropriately selected from inorganic or organic pigments and dyes.
Colorants that can be mixed to prepare black colorants include Victoria Pure Blue (42595), Auramine O (41000), Catilone Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), and Rhodamine B (45170). , Safranin OK 70:100 (50240), Erioglaucine X (42080), No. 120/Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla Fast Red 4015 (12355), Lionol Red 7B4401 (15850), First Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15:6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (Note that the numbers in parentheses above mean the color index (C.I.)).

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

Black colorants 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 these, conductive black colorants such as carbon black, acetylene black, and graphite can also be used to adjust the resistance value by being mixed.

As pigments, barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, chromium oxide, and the like can also be used. These various pigments can also be used in combination of multiple types.

The average particle diameter of the pigment used in the present invention is not particularly limited as long as the desired color can be developed when it is formed into a colored layer. preferably within the range of 10 to 70 nm. When the average particle size of the pigment is within the above range, the color characteristics of the liquid crystal display device manufactured using the photosensitive resin composition of the present invention can be of high quality.
The average particle size of the high resistance carbon black is preferably 60 nm or less, more preferably 50 nm or less, and preferably 20 nm or more. When the content is equal to or less than the above upper limit, scattering can be suppressed, and color characteristics such as light-shielding properties tend to be improved. Further, by setting the content to be not less than the above lower limit, excessive increase in the amount of the dispersant can be avoided, and the dispersibility tends to be improved.
The average particle size of the pigment can be obtained by directly measuring the size of primary particles from an electron micrograph. Specifically, the minor axis diameter and the major axis diameter of each primary particle are measured, and the average thereof is taken as the particle diameter of the particle. Next, for 100 or more particles, the volume (mass) of each particle is obtained by approximating the obtained particle size to a rectangular parallelepiped, and the volume average particle size is obtained and taken as the average particle size. The same result can be obtained by using either transmission type (TEM) or scanning type (SEM) electron microscope.

Moreover, the photosensitive resin composition of the present invention may contain a dye as another coloring material. Dyes that can be used in combination include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

Examples of azo dyes include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Mordan Tread 7, C.I. I. Mordant Yellow 5, C.I. I. mordant black 7 and the like.

Examples of anthraquinone dyes include C.I. I. bat blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 and the like can be mentioned.
In addition, as a phthalocyanine dye, for example, C.I. I. Pad Blue 5 and the like are quinone imine dyes, for example, C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes, for example, C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro-based dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Examples include Disperse Yellow 42 and the like.

(d) The content of the colorant is not particularly limited, but it can be usually selected in the range of 1 to 70% by mass based on the total solid content of the photosensitive resin composition. Within this range, 20% by mass or more is more preferable, 30% by mass or more is more preferable, 40% by mass or more is even more preferable, 45% by mass or more is particularly preferable, and 60% by mass or less is more preferable. When the content is equal to or higher than the lower limit, the light-shielding property tends to be improved, and when the content is equal to or lower than the upper limit, adhesion to the substrate tends to be improved. The combination of the upper limit and the lower limit is preferably 20-60% by mass, more preferably 30-60% by mass, even more preferably 40-60% by mass, even more preferably 45-60% by mass.

The content of the high-resistance carbon black (d1) is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more in the total solid content of the photosensitive resin composition. 40% by mass or more is more preferable, 45% by mass or more is particularly preferable, 50% by mass or more is most preferable, 70% by mass or less is preferable, and 60% by mass or less is more preferable. When the lower limit value or more is used, there is a tendency that both the light shielding property and the insulating property are easily compatible, and when the above upper limit value or less is used, the substrate adhesion and the insulating property tend to be easily compatible. The combination of the upper limit and the lower limit is preferably 10 to 70% by mass, more preferably 20 to 70% by mass, even more preferably 30 to 60% by mass, even more preferably 40 to 60% by mass, and 45 to 60% by mass. Especially preferred, 50 to 60% by mass is most preferred.

The content of carbon black constituting the high resistance carbon black (d1) is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass of the total solid content in the photosensitive resin composition. % or more, particularly preferably 45 mass % or more, preferably 60 mass % or less, more preferably 58 mass % or less, even more preferably 56 mass % or less, and particularly preferably 54 mass % or less. When the content is equal to or higher than the lower limit, the light-shielding property tends to be improved, and when the content is equal to or lower than the upper limit, adhesion to the substrate tends to be improved. The combination of the upper limit and the lower limit is preferably 20-60% by mass, more preferably 30-58% by mass, even more preferably 40-56% by mass, and even more preferably 45-54% by mass.

The content of carbon black constituting the high resistance carbon black (d1) in the (d) colorant is not particularly limited, but is preferably 60% by mass or more, more preferably 80% by mass or more, in the (d) colorant. It is preferably 90 mass % or more, more preferably 100 mass % or less. When the content is equal to or higher than the lower limit, there is a tendency that the light shielding property and the insulating property are improved.

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

In the photosensitive resin composition, the content of (d) the coloring material is usually 20 to 500 parts by mass, preferably 30 to 400 parts by mass, more preferably 40 to 350 parts by mass per 100 parts by mass of the alkali-soluble resin (a). It is in the range of parts by mass. When it is at least the above lower limit, it tends to be easy to suppress the deterioration of the solubility of the unexposed portion in the developer, and when it is at most the above upper limit, it tends to be easy to obtain the desired image thickness.

<(e) dispersant>
In the present invention, it is important to finely disperse (d) the coloring material and stabilize the dispersion state for ensuring the stability of the quality, so (e) dispersant is preferably included.
As the dispersant, a polymer dispersant having a functional group is preferable. Further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary, secondary or tertiary amino group. ; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine and pyrazine; Among them, polymer dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are particularly preferred. By using a polymer dispersant having these basic functional groups, there is a tendency that dispersibility can be improved and high light-shielding properties can be achieved.

Examples of polymer dispersants include urethane-based dispersants, acrylic dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ether-based dispersants. Dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants and the like can be mentioned.

Specific examples of such dispersants include trade names of EFKA (registered trademark, manufactured by EFKA Chemicals B.V. (EFKA)), Disperbyk (registered trademark, manufactured by BYK-Chemie), and Disparon (registered trademark, manufactured by Kusumoto Kasei). Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow or Floren (registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Fine-Techno Co., Ltd.) ), etc. can be mentioned.
One of these polymer dispersants may be used alone, or two or more thereof may be used in combination.

Among these, it is particularly preferable that (e) the dispersant contains a urethane polymer dispersant and/or an acrylic polymer dispersant having a basic functional group, from the viewpoint of adhesion and linearity. In particular, a urethane-based polymer dispersant is preferable in terms of adhesion. From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and a polyester bond and/or a polyether bond is preferred.

The weight-average molecular weight (Mw) of the polymeric dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less, more preferably 30,000 or less. When the amount is equal to or less than the above upper limit, alkali developability tends to be good even when the content of the coloring material is high.
Examples of urethane-based and acrylic-based polymer dispersants include Disperbyk 160-167, 182 series (all of which are urethane-based), Disperbyk 2000, 2001, etc. (both of which are acrylic-based) (all of which are manufactured by BYK-Chemie). Disperbyk 167, 182 and the like are particularly preferred urethane polymer dispersants having a polyester and/or polyether bond and having a weight average molecular weight of 30,000 or less.

<Urethane Polymer Dispersant>
Specific examples of preferred chemical structures for urethane-based polymer dispersants include, for example, a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule, and Dispersion resins having a weight-average molecular weight of 1,000 to 200,000, which are obtained by reacting active hydrogen with a compound having a tertiary amino group, and the like.

Examples of the above polyisocyanate compounds include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanate such as dimer acid diisocyanate, isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), ω,ω 1 ,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris(isocyanatophenylmethane), tris(isocyanatophenyl)thio Examples include triisocyanates such as phosphates, trimers thereof, water adducts, and polyol adducts thereof. Preferred polyisocyanates are trimers of organic diisocyanates, most preferred are trimers of tolylene diisocyanate and trimers of isophorone diisocyanate. These may be used individually by 1 type, and may use 2 or more types together.

As a method for producing a trimer of isocyanate, the above-mentioned polyisocyanates are treated with a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. to convert the isocyanate group part After the trimerization is terminated by adding a catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

Compounds having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and one terminal hydroxyl group of these compounds has 1 to 25 carbon atoms. and mixtures of two or more thereof.

Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more thereof. Examples of polyether diols include those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and these. and mixtures of two or more of

Polyetherester diols include those obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, e.g. oxytetramethylene) adipate and the like. The most preferred polyether glycols are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, and compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their 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-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol and other aliphatic glycols; bishydroxymethylcyclohexane and other aliphatic glycols; aromatic glycols such as lenglycol and bishydroxyethoxybenzene; N-alkyldialkanolamines such as N-methyldiethanolamine; , polyethylene/propylene adipate, etc., or polylactone diols or polylactone monools obtained by using the above diols or monohydric alcohols having 1 to 25 carbon atoms as initiators, such as polycaprolactone glycol, polymethylvalerolactone and these Mixtures of two or more are included. The most preferred polyester glycol is polycaprolactone glycol or polycaprolactone initiated by an alcohol having 1 to 25 carbon atoms.

Examples of polycarbonate glycols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate, and examples of polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. are mentioned.
These may be used individually by 1 type, and may use 2 or more types together.

The compound having one or two hydroxyl groups in the molecule generally has a number average molecular weight of 300 to 10,000, preferably 500 to 6,000, more preferably 1,000 to 4,000.
A compound having an active hydrogen and a tertiary amino group in the molecule used in the present invention will be explained. Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. A hydrogen atom of the amino group of is preferred.

The tertiary amino group is not particularly limited, but includes, for example, an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically an imidazole ring or a triazole ring.
Examples of such compounds having active hydrogen and a tertiary amino group in the molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 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.

Further, when the tertiary amino group is a nitrogen-containing heterocyclic structure, the nitrogen-containing heterocyclic ring includes a pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo N-containing hetero 5-membered rings such as triazole ring, benzoxazole ring, benzothiazole ring and benzothiadiazole ring; nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline ring ring. Preferred among these nitrogen-containing heterocycles are imidazole rings and triazole rings.

Specific examples of compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, 1-(2-aminoethyl)imidazole and the like. Specific examples of compounds having a triazole ring and an amino group include 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 them, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3-amino-1,2,4-triazole preferable.

These may be used individually by 1 type, and may use 2 or more types together.
The preferred blending ratio of raw materials when producing a urethane polymer dispersant is 10 to 200 mass parts of a compound having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the molecule per 100 mass parts of a polyisocyanate compound. parts, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass of a compound having active hydrogen and a tertiary amino group in the molecule is.

The urethane polymer dispersant is produced according to a known method for producing polyurethane resins. Solvents used in the production generally include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone, esters such as ethyl acetate, butyl acetate, and cellosolve acetate, benzene, toluene, xylene, and hexane. Some alcohols such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethylsulfoxide are used. These may be used individually by 1 type, and may use 2 or more types together.

A urethanization reaction catalyst is usually used for the above production. Examples of this catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and stannus octoate; iron-based catalysts such as iron acetylacetonate and ferric chloride; One or two or more types such as class amines may be used.

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

Amine value [mgKOH/g] = (561 x V)/(W x S)
[However, W: Amount of weighed dispersant sample [g], V: Amount of titration [mL] at the end point of titration, S: Solid content concentration [% by mass] of dispersant sample. ]
The introduction amount of the compound having active hydrogen and tertiary amino group in the molecule is preferably controlled in the range of 1 to 100 mgKOH/g in terms of amine value after the reaction. More preferably, it is in the range of 5-95 mgKOH/g. The amine value is a value expressed in mg of KOH corresponding to the acid value obtained by neutralizing and titrating the basic amino group with an acid. When the amine value is above the lower limit, the dispersibility tends to be good, and when the amine value is below the upper limit, the developability tends to be good.

When the isocyanate group remains in the polymer dispersant after the reaction described above, it is preferable to crush the isocyanate group with an alcohol or an amino compound, since the stability of the product over time increases.
The weight-average molecular weight (Mw) of the urethane polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. 30000 or less is especially preferable. The dispersibility and dispersion stability tend to be improved by setting the amount to the lower limit or more, and the solubility tends to be improved by setting the amount to the upper limit or less. When the molecular weight is 30,000 or less, the alkali developability tends to be good even when the coloring material content is particularly high. Examples of such particularly preferred commercially available urethane dispersants include Disperbyk 167 and 182 (Byk-Chemie).

When the photosensitive resin composition of the present invention contains (e) a dispersant, the content of (e) dispersant is usually 50% by mass or less, preferably 30% by mass, in the total solid content of the photosensitive resin composition. % 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, particularly preferably 10 mass % or more. The combination of the upper limit and the lower limit is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, even more preferably 5 to 20% by mass, even more preferably 7 to 20% by mass, and 10 to 20% by mass. Especially preferred.
By setting it to the above lower limit or more, there is a tendency to ensure sufficient dispersibility, and by setting it to the above upper limit or less, color density, sensitivity, film formation properties, etc. can be improved without reducing the proportion of other components. It tends to be good enough.

The content 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, relative to 100 parts by mass of the (d) coloring material. , preferably 80 parts by mass or less, more preferably 50 parts by mass or less. A 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.
By setting it to the above lower limit or more, there is a tendency to easily secure sufficient dispersibility, and by setting it to the above upper limit or less, color density, sensitivity, film formation properties, etc. can be improved without reducing the proportion of other components. It tends to be good enough.

<Thiols>
The photosensitive resin composition of the present invention preferably contains thiols in order to increase sensitivity and improve adhesion to substrates. Examples of thiols include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate. , butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, Ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate) (PGMB for short), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy ) Butane (trade name: Karenz MT BD1, manufactured by Showa Denko), butanediol trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate) (trade name: Karenz MT PE1, Showa Denko company), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate) ), trimethylolpropane tris(3-mercaptobutyrate) (TPMB for short), trimethylolpropane tris(2-mercaptoisobutyrate) (TPMIB for short), 1,3,5-tris(3-mercaptobutyloxy ethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (trade name: Karenz MT NR1, manufactured by Showa Denko Co., Ltd.), and the like. A seed|species can be used individually or in mixture of 2 or more types. Preferably, polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1 are preferred. Especially preferred.

When a thiol compound is used, the content of the thiol compound is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, more preferably 0.3% by mass or more, in the total solid content of the photosensitive resin composition of the present invention. It is 0.5% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less. When it is at least the above lower limit, it tends to be possible to suppress a decrease in sensitivity, and when it is at most the above upper limit, there tends to be a tendency to improve the storage stability.

<Solvent>
The photosensitive resin composition of the present invention usually comprises (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, (d) a coloring material and various components used as necessary. is used in a state of being dissolved or dispersed in an organic solvent.
As the organic solvent, it is preferable to select one having a boiling point (under a pressure of 1013.25 [hPa]; hereinafter, the same applies to all boiling points) in the range of 100 to 300°C. A solvent having a boiling point of 120 to 280° C. is more preferred.
Examples of such organic solvents include the following.

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-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl glycol monoalkyl ethers such as ethers, triethylene glycol monoethyl ether, tripropylene glycol methyl ether;

glycol dialkyl ethers 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;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl 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 monoethyl glycol alkyl ether acetates such as ether acetate, 3-methyl-3-methoxybutyl acetate;

Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
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 butyl ketone, methylhexyl ketone, methyl nonyl ketone, methoxymethyl pentanone ketones;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Chain or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

Halogenated hydrocarbons such as butyl chloride, amyl chloride;
ether ketones such as methoxymethylpentanone;
Acetonitrile, nitriles such as benzonitrile, etc.:
Commercially available solvents corresponding to the above include Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and no. 2, Solvesso #150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (“cellosolve” is a registered trademark. The same shall apply hereinafter.), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (any are also trade names).

These organic solvents may be used alone or in combination of two or more.
When forming pixels of a color filter or a black matrix by photolithography, it is preferable to select an organic solvent having a boiling point in the range of 100 to 250°C. More preferably, it has a boiling point of 120-230°C.
Among the above organic solvents, glycol alkyl ether acetates are preferable because they have a good balance of applicability, surface tension, etc., and relatively high solubility of the components in the composition.

Also, the glycol alkyl ether acetates may be used alone, or may be used in combination with other organic solvents. Glycol monoalkyl ethers are particularly preferred as other organic solvents that may be used in combination. Among them, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituents in the composition. Glycol monoalkyl ethers have a high polarity, and if the amount added is too large, the pigment tends to aggregate, and the viscosity of the subsequently obtained photosensitive resin composition tends to decrease, resulting in a decrease in storage stability. , the ratio of the glycol monoalkyl ether in the solvent is preferably 5% by mass to 30% by mass, more preferably 5% by mass 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”). The combined use of such a high boiling point solvent makes the photosensitive resin composition difficult to dry, but has the effect of preventing the uniformly dispersed state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of foreign matter defects due to deposition and solidification of the coloring material at the tip of the slit nozzle. From the point that such an effect is high, among the above-mentioned various solvents, dipropylene glycol methyl ether acetate, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1, 3-butylene glycol diacetate, triacetin, 1,6-hexanediol diacetate are preferred.

When a high boiling point solvent is used in combination, the content of the high boiling point solvent in the organic solvent is preferably 0% by mass to 50% by mass, more preferably 0.5% by mass to 40% by mass, and 1% by mass to 30% by mass. is particularly preferred. By making it equal to or higher than the above lower limit, there is a tendency to suppress, for example, the deposition and solidification of a coloring material at the tip of a slit nozzle and causing foreign matter defects. can be suppressed from becoming too slow, and it tends to be easy to avoid the occurrence of problems such as takt failure in the reduced pressure drying process and pre-baking pin marks in the color filter manufacturing process.

In the photosensitive resin composition of the present invention, the content of the organic solvent is not particularly limited, but from the viewpoint of ease of application and viscosity stability, the total solid content in the photosensitive resin composition is preferably 5% by mass or more, More preferably 8% by mass or more, still more preferably 10% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, particularly preferably 20% by mass or less. It is prepared as follows. The combination of the upper limit and the lower limit is preferably 5-40% by mass, more preferably 8-30% by mass, still more preferably 10-25% by mass, and particularly preferably 10-20% by mass.

<Other compounding components of the photosensitive resin composition>
In the photosensitive resin composition of the present invention, in addition to the components described above, an adhesion improver, a coatability improver, a pigment derivative, a development improver, an ultraviolet absorber, an antioxidant, and the like can be appropriately blended.

<Adhesion improver>
In order to improve the adhesion to the substrate, an adhesion improver may be included, such as a silane coupling agent, a titanium coupling agent, etc., but 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, X-12-1050 (manufactured by Shin-Etsu Silicone Co., Ltd.), Z-6040, Z-6043, Z-6062 (manufactured by Dow Corning Toray Co., Ltd.) and the like. In addition, 1 type may be used for a silane coupling agent, and 2 or more types may be used together by arbitrary combinations and ratios.
Further, an adhesion improver other than the silane coupling agent may be contained in the photosensitive resin composition of the present invention, and examples thereof include a phosphoric acid-based adhesion improver and other adhesion improvers.

As the phosphoric acid-based adhesion improver, (meth)acryloyloxy group-containing phosphates are preferable, and among them, those represented by the following general formulas (g1), (g2), and (g3) are preferable.

In general formulas (g1), (g2) and (g3) above, each R ⁵¹ independently represents a hydrogen atom or a methyl group. l and l' each independently represent an integer of 1 to 10; m each independently represents 1, 2 or 3;
Other adhesion improvers include TEGO (registered trademark) Add Bond LTH (manufactured by Evonik). These phosphoric acid group-containing compounds and other adhesion agents may be used alone or in combination of two or more.

The content of the adhesion improver 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, more preferably 0.10% by mass or more, based on the total solid content. It is more preferably 50% by mass or more, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and even more preferably 2.0% by mass or less. , 1.5% by mass or less. Adhesion strength tends to improve when the content is equal to or higher than the lower limit, and developability tends to be improved when the content is equal to or lower than the upper limit.

<Applicability improver>
The photosensitive resin composition of the present invention may contain a surfactant as a coatability improver in order to improve coatability. Various surfactants such as anionic, cationic, nonionic and amphoteric surfactants can be used as surfactants. Among them, it is preferable to use nonionic surfactants because they are less likely to adversely affect various properties. Among them, fluorine-based or silicone-based surfactants are effective in terms of coatability.

Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie), KP340. (manufactured by Shin-Etsu Silicone Co., Ltd.), Megafac F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Dow Corning Toray), DS-401 (Daikin) ), L-77 (manufactured by Nippon Unicar) and FC4430 (manufactured by 3M Japan). In addition, 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.
When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant in the photosensitive resin composition is not particularly limited, but 0.01 in the total solid content of the photosensitive resin composition It is preferably at least 0.05% by mass, more preferably at least 0.05% by mass, preferably at most 1.0% by mass, more preferably at most 0.7% by mass, and 0 It is more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less. When the concentration is equal to or higher than the above lower limit, coating uniformity tends to be improved. 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 0.05 to 0.05% by mass. 0.3% by weight is particularly preferred.

<Pigment derivative>
The photosensitive resin composition of the present invention may contain a pigment derivative in order to improve dispersibility and storage stability. Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, and dioxazine. Among them, phthalocyanine-based and quinophthalone-based derivatives are preferred.

Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, and the like, which may be directly attached to the pigment skeleton or may be attached to the skeleton of the pigment. Examples thereof include those bonded via a ring group or the like, preferably a sulfonic acid group. A single pigment skeleton may be substituted with a plurality of these substituents. Specific examples of pigment derivatives include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. These may be used individually by 1 type, and may use 2 or more types together.
The pigment derivative is preferably used together with a dispersant.

When the photosensitive resin composition of the present invention contains a pigment derivative, the content of the pigment derivative in the photosensitive resin composition is not particularly limited, but the total solid content of the photosensitive resin composition is 0.1% by mass. 0.5% by mass or more is more preferable, 1.0% by mass or more is even more preferable, and 10% by mass or less is preferable, and 5% by mass or less is more preferable. When the content is equal to or higher than the lower limit, the dispersion stability tends to be improved, and when the content is equal to or lower than the upper limit, the developability tends to be improved. A 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 the photosensitive resin composition>
The photosensitive resin composition of the present invention can be suitably used for forming a black matrix, and from such a viewpoint, it preferably exhibits a black color. Further, the optical density (OD) per 1 μm of film thickness of the cured film is preferably 1.0 or more, more preferably 2.0 or more, further preferably 2.5 or more, and 3 It is more preferably 0.0 or more, particularly preferably 4.0 or more, most preferably 4.5 or more, and usually 6.0 or less. By making it equal to or higher than the lower limit, there is a tendency that sufficient light shielding properties can be ensured.

<Method for producing a photosensitive resin composition>
The photosensitive resin composition of the present invention is produced according to a conventional method.
Generally, (d) coloring material is preferably dispersed in advance using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like. Since the coloring material (d) is finely divided by the dispersion treatment, the application properties of the photosensitive resin composition are improved. In addition, when a black colorant is used as the colorant (d), it contributes to the improvement of the light shielding ability.

Dispersion treatment is usually preferably carried out in a system in which (d) a coloring material, an organic solvent, and optionally (e) a dispersant and (a) a part or all of an alkali-soluble resin are used in combination (hereinafter referred to as The mixture subjected to the dispersion treatment and the composition obtained by the treatment are sometimes referred to as "ink" or "pigment dispersion"). In particular, it is preferable to use a polymer dispersant as the dispersant, since the resulting ink and photosensitive resin composition are prevented from thickening over time (excellent in dispersion stability).
When dispersion treatment is performed on a liquid containing all the components to be blended in the photosensitive resin composition, highly reactive components may be denatured due to heat generated during the dispersion treatment. Therefore, it is preferable to carry out the dispersion treatment in a system containing a polymer dispersant.

When dispersing (d) the coloring material with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. As for the dispersion treatment conditions, the temperature is usually from 0°C to 100°C, preferably from room temperature to 80°C. The appropriate dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment apparatus, etc., and is therefore adjusted as appropriate. The index of dispersion is to control the glossiness of the ink so that the 20 degree specular glossiness (JIS Z8741) of the photosensitive resin composition is in the range of 100-200. When the glossiness of the photosensitive resin composition is low, dispersion processing is often insufficient and rough pigment (coloring material) particles remain, resulting in insufficient developability, adhesion, resolution, etc. there is a possibility. Further, if the dispersion treatment is carried out until the gloss value exceeds the above range, the pigment is crushed to produce a large number of ultrafine particles, which tends to impair the dispersion stability.

Next, the ink obtained by the dispersion treatment and the other components contained in the photosensitive resin composition are mixed to form a uniform solution. In the production process of the photosensitive resin composition, fine dust is often mixed in the liquid, so it is desirable to filter the obtained photosensitive resin composition with a filter or the like.

[Cured product]
The cured product of the invention is obtained by curing the photosensitive resin composition of the invention. A cured product obtained by curing the photosensitive resin composition can be suitably 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 comprising the cured product of the present invention and the color filter containing the black matrix of the present invention will be described according to the production method thereof.

(1) Support The material of the support for forming the black matrix is not particularly limited as long as it has an appropriate strength. Transparent substrates are mainly used, and the materials include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, and epoxy resins. , unsaturated polyester resin, thermosetting resin sheet such as poly(meth)acrylic resin, or various glasses. Among these, glass and heat-resistant resin are preferable from the viewpoint of heat resistance. In some cases, a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Besides the transparent substrate, it can also be formed on a TFT array.

In order to improve surface physical properties such as adhesiveness, if necessary, the support may be subjected to corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, silane coupling agent, or thin film formation treatment using various resins such as urethane resins. may be performed.
The thickness of the transparent substrate is usually in the range of 0.05-10 mm, preferably 0.1-7 mm. When thin films of various resins are formed, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

(2) Black Matrix In order to form the black matrix of the present invention from the above-described photosensitive resin composition of the present invention, the photosensitive resin composition of the present invention is coated on a transparent substrate, dried, and then the sample. A photomask is placed thereon, and a black matrix is formed by imagewise exposure through the photomask, development, and heat curing or photocuring as required.

(3) Formation of black matrix (3-1) Application of photosensitive resin composition The photosensitive resin composition for the black matrix can be applied onto the transparent substrate by spinner method, wire bar method, flow coat method or die coat method. , a roll coating method, a spray coating method, or the like. Above all, according to the die coating method, the amount of coating liquid used is greatly reduced, and there is no effect of mist that adheres when using the spin coating method, and the generation of foreign matter is suppressed. preferred from

The thickness of the coating film after drying is usually preferably in the range of 0.2 to 10 μm, more preferably in the range of 0.5 to 6 μm, and still more preferably in the range of 1 to 4 μm. be. By making it below the said upper limit, there exists a tendency for pattern development to become easy and to become easy to adjust the gap in a liquid-crystal cell-forming process. By making it more than the said lower limit, there exists a tendency for desired color expression to become easy.

(3-2) Drying of Coating Film Drying of the coating film after applying the photosensitive resin composition to the substrate is preferably by a drying method using a hot plate, an IR oven, or a convection oven. The drying conditions can be appropriately selected depending on the type of the solvent component, the performance of the dryer to be used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably at a temperature of 50 to 130 ° C., depending on the type of solvent component, the performance of the dryer used, etc. It is selected in the range of 30 seconds to 3 minutes.

The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. In addition, the drying process of this coating film may be a reduced pressure drying method in which the drying is performed in a reduced pressure chamber without increasing the temperature.

(3-3) Exposure Imagewise exposure is carried out by overlaying a negative mask pattern on the coating film of the photosensitive resin composition and irradiating light of wavelengths from the ultraviolet region to the visible region through this mask pattern. In this case, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, the exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film. The light source used for the above image exposure is not particularly limited. Examples of light sources include lamp light sources such as 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 arcs. An optical filter can also be used when using it by irradiating the light of a specific wavelength.

(3-4) Development The black matrix according to the present invention is prepared by subjecting a coating film made of a photosensitive resin composition to imagewise exposure with the light source described above, followed by an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. can be produced by forming an image on the substrate by development with This aqueous solution may further contain organic solvents, buffers, complexing agents, dyes or pigments.

Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate. , sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, inorganic alkaline compounds such as ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or trimethylamine , mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. compound. These alkaline compounds may be a mixture of two or more.

Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; Anionic surfactants such as salts, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinate ester salts, and amphoteric surfactants such as alkylbetaines and amino acids.

Examples of organic solvents include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. The organic solvent may be used alone or in combination with an aqueous solution.
The conditions for the development treatment are not particularly limited, and the development temperature is usually in the range of 10 to 50°C, especially 15 to 45°C, particularly preferably 20 to 40°C. Any method such as a development method or an ultrasonic development method can be used.

(3-5) Heat Curing Treatment The substrate after development is subjected to heat curing treatment or photocuring treatment, preferably heat curing treatment. At this time, the heat curing treatment conditions are selected within a temperature range of 100 to 280° C., preferably 150 to 250° C., and a time range of 5 to 60 minutes.
The height of the black matrix formed as described above is usually 0.5 to 5 μm, preferably 0.8 to 4 μm.
Furthermore, the optical density (OD) per 1 μm of thickness is 2.0 or more, preferably 2.5 or more, more preferably 3.0 or more, and particularly preferably 3.2 or more.

On a transparent substrate provided with a black matrix, a photosensitive resin composition containing a coloring material of one of red, green, and blue is applied in the same process as (3-1) to (3-5) above, and dried. After that, a photomask is overlaid on the coating film, imagewise exposure through the photomask, development, and if necessary, thermal curing or photocuring are performed to form a pixel image, thereby forming a colored layer. A color filter image can be formed by performing this operation for each of the three photosensitive resin compositions of red, green, and blue. These orders are not limited to the above.

The photosensitive resin composition of the present invention can also be used as a photosensitive resin composition for colored spacers in addition to the black matrix. When spacers are used in TFT-type LCDs, the TFTs may malfunction as switching elements due to light incident on the TFTs. Colored spacers are used to prevent this. JP-A-2003-110002 describes that the spacer is light-shielding. The colored spacers can be formed in the same manner as the black matrix described above, except that a mask for colored spacers is used.

(3-6) Formation of transparent electrodes The color filter is used as a part of parts such as color displays and liquid crystal display devices by forming transparent electrodes such as ITO on the image in this state. A topcoat layer of polyamide, polyimide, or the like may be provided on the image, if necessary, in order to improve the properties and durability. In addition, in some applications such as planar alignment driving system (IPS mode), the transparent electrode may not be formed.

[Image display device]
The image display device of the present invention has the cured product of the present invention, and includes, for example, the black matrix of the present invention. The image display device is not particularly limited as long as it is a device that displays an image or video, and examples thereof include a liquid crystal display device and an organic EL display, which will be described later.

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

In a liquid crystal display device, an alignment film is usually formed on a color filter, spacers are sprinkled on the alignment film, and then bonded to a counter substrate to form a liquid crystal cell, liquid crystal is injected into the formed liquid crystal cell, It is completed by connecting to the counter electrode. As the alignment film, a resin film such as polyimide is suitable. A gravure printing method and/or a flexographic printing method is usually employed for forming the alignment film, and the thickness of the alignment film is set to several tens of nanometers. After hardening the alignment film by heat baking, the surface is treated by irradiation with ultraviolet rays or treatment with a rubbing cloth, so that the surface state is processed so that the tilt of the liquid crystal can be adjusted.

As the spacer, a spacer having a size corresponding to the gap (clearance) with the opposing substrate is used, and a spacer of 2 to 8 μm is usually suitable. A photospacer (PS) made of a transparent resin film can be formed on the color filter substrate by photolithography and used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly suitable.

The gap between the opposing substrate and the bonding substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After bonding to the opposing substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and/or heating to seal the periphery of the liquid crystal cell.
After the liquid crystal cell with its periphery sealed is cut into panels, the pressure is reduced in a vacuum chamber, the liquid crystal inlet is immersed in the liquid crystal, and then the chamber is leaked to inject 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, preferably 1×10 ^-3 to 1×10 ^-6 Pa. Moreover, it is preferable to heat the liquid crystal cell when the pressure is reduced, and the heating temperature is usually 30 to 100.degree. Heating and holding at reduced pressure is usually in the range of 10 to 60 minutes, and then immersed in liquid crystal. A liquid crystal display device (panel) is completed by sealing the liquid crystal injection port of the liquid crystal cell into which the liquid crystal is injected by curing the UV curing resin.

There are no particular restrictions on the type of liquid crystal, and any known liquid crystal such as aromatic, aliphatic, polycyclic compounds, lyotropic liquid crystal, thermotropic liquid crystal, or the like may be used. Thermotropic liquid crystals include nematic liquid crystals, smestic liquid crystals, cholesteric liquid crystals, and the like, and any of them may be used.

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

When producing an organic EL display using the color filter of the present invention, for example, as shown in FIG. A color filter is prepared by forming a resin black matrix (not shown) provided between the pixels 20, and an organic light emitter 500 is formed on the color filter with an organic protective layer 30 and an inorganic oxide film 40 interposed therebetween. The organic EL element 100 can be produced by laminating the . At least one of the pixels 20 and the resin black matrix is manufactured using the photosensitive resin composition of the present invention. As a method of stacking the organic light emitter 500, a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter, or , a method of bonding the organic light emitter 500 formed on another substrate onto the inorganic oxide film 40, and the like. Using the organic EL element 100 produced in this way, for example, the method described in "Organic EL Display" (Ohmsha, August 20, 2004, Shizuo Tokito, Chihaya Adachi, Hideyuki Murata), etc. , an organic EL display can be produced.

The color filter of the present invention can be applied to both a passive drive type organic EL display and an active drive type organic EL display.

EXAMPLES Next, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
In addition, the volume resistivity of the coloring material was measured by the following procedure.

(Measurement of volume resistivity of coloring material)
First, about 2 g of a sample is placed in a Teflon (registered trademark) container with an inner diameter of 2 cm with a brass electrode attached to the bottom, and the tip is covered with a Teflon rod with a brass electrode. /min and held at 50 kg/cm ² for 1 minute, the current was set to 1 mA and the resistance was measured with a highly sensitive tester. Then, from the bulkiness and resistance value of the powder (coloring material) under this load, the volume resistivity was calculated by the following formula.

Volume resistivity (Ω cm) =
Cross-sectional area of powder (cm ² ) × resistance value (Ω)/bulk height of powder (cm)

<Preparation of coated carbon black 1>
Coated carbon black 1 was prepared by the method described in Production Example 1 of Japanese Patent Application Laid-Open No. 2013-195538. As 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 Co., Ltd., carbon black) is placed in a cylindrical kiln with an inner diameter of 10 cm and a length of 10 cm, and is rotated at 9 rpm while being brought into contact with a mixed gas of air and ozone (6000 ppm of ozone) for 3 hours. Oxidation treatment was performed. Then, 60 g of the above carbon black was dispersed in 1300 g of pure water. Furthermore, after adding 1.1 g of a curing agent (IBMI12 (manufactured by Mitsubishi Chemical Co.)) to a resin solution (jER154 (manufactured by Mitsubishi Chemical Co.): 5.6 g, toluene: 60 mL) dissolved in toluene and sufficiently dissolving, 600 mL of water and 120 mL of ethanol were added and stirred at 9000 rpm for 30 minutes with a homogenizer to prepare a resin emulsion. Next, the above resin emulsion was gradually added to the carbon black dispersion stirred with a screw to coat the surface of the carbon black with the resin. Then, the mixture was heated while stirring, and a curing treatment was performed at 70° C. for 4 hours after the toluene had evaporated. After removing the water by filtration, it was placed in a vacuum drying container and dried at 62° C. for 10 hours to remove the water and solvent to obtain Coated Carbon Black 2 .
The volume resistivity of the coated carbon black 2 was measured according to the above (measurement of volume resistivity of coloring material) and found to be 15.33 Ω·cm.

<Preparation of coated carbon black ink 1>
Using the coated carbon black 1 prepared in <Preparation of coated carbon black 1>, the coated carbon black ink 1 having a solid content of 25% by mass is prepared by the method described in Production Example 2 of Japanese Patent Application Laid-Open No. 2013-195538. was prepared. As the dispersant, DISPERBYK-167 (manufactured by BYK-Chemie, basic urethane dispersant) was used.

The mass ratio of each component of the obtained coated carbon black ink 1 is as follows.
・ Pigment / MA77 (manufactured by Mitsubishi Chemical Co., carbon black): 18.0 parts by mass ・ Coating resin / jER (registered trademark) 828 (manufactured by Mitsubishi Chemical Co., epoxy resin): 2.0 parts by mass ・ Dispersant / DISPERBYK- 167 (manufactured by BYK Chemie, basic urethane dispersant): 4.4 parts by mass Dispersing aid (pigment derivative) / Solsperse 12000 (manufactured by Lubrizol, phthalocyanine pigment derivative having an acidic group): 1.0 parts by mass Solvent/propylene glycol monomethyl ether acetate (PGMEA): 76.2 parts by mass

<Preparation of coated carbon black ink 2>
Except for using the coated carbon black 2 prepared in the <Preparation of coated carbon black 2> instead of the coated carbon black 1 in <Preparation of coated carbon black ink 1><Covered carbon black ink 1>Preparation>, coated carbon black ink 2 was prepared.

<Preparation of carbon black ink>
In <Preparation of coated carbon black ink 1>, MA77 (manufactured by Mitsubishi Chemical Corporation, carbon black ) was prepared in the same manner as <Preparation of coated carbon black ink 1>, except that 18.0 parts by mass was used.
When the volume resistivity of MA77 was measured according to the above (measurement of volume resistivity of coloring material), it was 1.69 Ω·cm.

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

50 g of the epoxy compound having the above structure (epoxy equivalent weight: 264), 13.65 g of acrylic acid, 60.5 g of 3-methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of para-methoxyphenol were mixed with a thermometer, a stirrer, and a condenser. was placed in a flask equipped with , and the mixture was reacted at 90° C. with stirring until the acid value became 5 mgKOH/g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
25 parts by mass of the resulting 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) A part by mass was placed in a flask equipped with a thermometer, a stirrer and a cooling tube, and the temperature was slowly raised to 105° C. while stirring to cause a reaction.
When the resin solution became transparent, it was diluted with 3-methoxybutyl acetate (MBA) and prepared so that the solid content was 50% by mass. ) 2600 of alkali-soluble resin (1) was obtained.

<Synthesis Example 2: Synthesis of alkali-soluble resin (2)>

7.3 g of the epoxy compound having the above chemical structure (epoxy equivalent weight: 240), 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 were mixed with a thermometer and a stirrer. , and put into a flask equipped with a cooling tube, and reacted with stirring at 100°C until the acid value became 5 mgKOH/g or less. The reaction took 9 hours to obtain an epoxy acrylate solution.
16 parts by mass of the resulting 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) parts, and 14 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) are placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and slowly heated to 105 ° C. while stirring to react, solid content 40% by mass, An alkali-soluble resin (2) having an acid value of 100 mgKOH/g and a polystyrene equivalent weight average molecular weight (Mw) of 10400 measured by GPC was obtained.

<Photoinitiator (1)>

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

<Photoinitiator (2)>

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

<Photoinitiator (3)>

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

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

<Adhesion improver>
As the adhesion improver, KBM-5103 (3-acryloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., which is a silane coupling agent, was used.
<Applicability improver>
Megafac F-554 (fluorine-containing group/lipophilic group-containing oligomer, nonionic surfactant) manufactured by DIC Corporation was used as a coating property improver.

<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 the proportions shown in Table 1 were obtained, and the ingredients were stirred and dissolved with a stirrer to prepare black resist 1. bottom. The total solid content in Black Resist 1 is 14 mass %.

The abbreviations of solvents in Table 1 have the following meanings.
PGMEA: propylene glycol monomethyl ether acetate.
MBA: 3-methoxybutyl acetate.

<Example 2>
(Preparation of black resist 2)
In Black Resist 1, the content ratio of carbon black in the total solid content was lowered to 40% by mass, and the content ratio of other components in the total solid content was changed to the values shown in Table 2. A black resist 2 having a total solids content of 14% by mass was prepared in the same manner as for black resist 1.

<Example 3>
(Preparation of black resist 3)
In Black Resist 1, the content ratio of the photopolymerization initiator in the total solid content was lowered to 3.0% by mass, and the content ratio of other components in the total solid content was changed to the values shown in Table 2. A black resist 3 having a total solids content of 14% by mass was prepared in the same manner as for the black resist 1, except for the above.

<Example 4>
(Preparation of black resist 4)
In black resist 1, coated carbon black ink 2 was used instead of coated carbon black ink 1, and the content of other components in the total solid content was changed to the values shown in Table 2. A black resist 4 having a total solids content of 14% by mass was prepared in the same manner as for resist 1.

<Comparative Example 1>
(Preparation of black resist 5)
Black resist 5 having a total solid content of 14% by mass was prepared in the same manner as in black resist 1, except that photopolymerization initiator (1) in black resist 1 was changed to photopolymerization initiator (2). bottom.

<Comparative Example 2>
(Preparation of black resist 6)
Black resist 6 having a total solid content of 14% by mass was prepared in the same manner as in black resist 1, except that the photopolymerization initiator (1) in black resist 1 was changed to photopolymerization initiator (3). bottom.

<Comparative Example 3>
(Preparation of black resist 7)
In Black Resist 1, Carbon Black Ink 3 was used instead of Coated Carbon Black Ink 1, and the contents of other components in the total solid content were changed to the values shown in Table 2. A black resist 7 having a total solid content of 14% by mass was prepared in the same manner as in 1.

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

(Evaluation of photosensitive resin composition)
(1) Preparation of Black Resist Cured Film The prepared black resists 1 to 8 were applied to a glass substrate using a spin coater, dried under reduced pressure, and then dried using a hot plate at 100° C. for 120 seconds. The coating conditions were adjusted so that the film thickness after coating and drying was about 1.2 μm. Subsequently, the resulting dried coating film was exposed using an exposure machine (EXF-2829-F-00 manufactured by Oak Manufacturing Co., Ltd.) using a high-pressure mercury lamp (ADH-3000M-FN manufactured by Oak Manufacturing Co., without an optical filter). The entire surface was exposed at 40 mJ/cm ² without an exposure mask. After that, at room temperature (23° C.), a KOH aqueous solution adjusted to 0.04% by mass with ultrapure water is used as an alkaline developer, and spray development is performed for 2.0 times the dissolution time (spray pressure: 0.1 MPa). Then, spray cleaning with ultrapure water (spray pressure: 0.1 MPa) was performed to obtain a black resist film. After that, heat curing was performed in an oven at 230° C. for 30 minutes to form a cured black resist film having a thickness of 1.0 μm. The dissolution time is the time during which the unexposed portion of the photosensitive layer dissolves and the surface of the substrate begins to be visible during development, and the dissolution time of each black resist was 30 to 50 seconds.
The film thickness of the cured black resist film was measured with a step measurement device Alpha-Step-500 (manufactured by KLA-Tencor) after a portion of the film was cut with a cutter to provide a step portion. Incidentally, the film thickness can be adjusted by changing the rotation speed of the spin coater.

(2) Preparation of black matrix (BM) cured film For the dry coating film obtained in the same procedure as in (1) above, using an exposure machine (EXF-2829-F-00 manufactured by Oak Manufacturing Co., Ltd.), a high-pressure mercury lamp (ADH-3000M-FN, no optical filter, manufactured by ORC Manufacturing Co., Ltd.) at 40 mJ/cm ² , pattern exposure (proximity gap 180 μm) was performed through an exposure mask having a linear opening with a width of 20 μm. After that, at room temperature (23° C.), a KOH aqueous solution adjusted to 0.04% by mass with ultrapure water is used as an alkaline developer for a time 1.8 times the dissolution time, and spray development is performed (spray pressure: 0.1 MPa). Then, it was spray-washed with ultrapure water (spray pressure: 0.1 MPa) to obtain a BM film. After that, heat curing was performed in an oven at 230° C. for 30 minutes to prepare a BM cured film having a thickness of 1.0 μm.

(3) Sensitivity Evaluation As the exposure sensitivity of the black resist increases, the line width of the formed BM fine lines tends to increase. Sensitivity was evaluated by measuring the line width of the BM thin line in the BM cured film with an optical microscope. Table 3 shows the measurement results.

(4) OD measurement The light-shielding property (optical density, OD) of the cured black resist film was measured with a transmission density measuring device GretagMacbeth D200-II (manufactured by GretagMacbeth). By dividing the OD by the film thickness, the OD (unit OD) per 1 μm film thickness was obtained. Table 3 shows the measurement results.

(5) Measurement of Volume Resistivity Each of the prepared black resists 1 to 8 was applied to a chromium (Cr)-evaporated glass substrate using a spin coater, dried under reduced pressure, and dried on a hot plate at 100° C. for 120 seconds. The coating conditions were adjusted so that the film thickness after heat curing was 3.0 μm. Subsequently, the resulting dried coating film was exposed using an exposure machine (EXF-2829-F-00 manufactured by Oak Manufacturing Co., Ltd.) using a high-pressure mercury lamp (ADH-3000M-FN manufactured by Oak Manufacturing Co., without an optical filter). The entire surface was exposed at 40 mJ/cm ² without an exposure mask. Thereafter, heat curing was performed in an oven at 230° C. for 180 minutes to form a cured black resist film having a thickness of 3.0 μm. Using the chromium vapor deposition film of this sample as the main electrode and the gold (Au) film formed by vapor deposition on the black resist cured film as the counter electrode, an applied voltage ( Direct current) The volume resistivity was obtained by measuring the current values at 1V and 10V. Table 3 shows the measurement results.

Table 3 shows the following.
Unit OD: Examples 1, 3 to 4, and Comparative Examples 1 to 4 having the same carbon black content show the same OD value, so there is no difference in the residual film rate after heat curing in each cured film. I understand.
Sensitivity: In Example 1, the line width of the 20 μm pattern was 1 μm or more thicker than in Comparative Example 1, and the sensitivity was good. Also, in Comparative Example 2, the line width of the 20 μm pattern was narrowed to 11 μm, and a large decrease in sensitivity was observed.

Volume resistivity: Comparative Example 1 shows a high resistance value on the order of 10 13 at a measurement voltage of 1V, but at a measurement voltage of 10V it shows a large drop of two digits. Further, Comparative Example 2 showed a higher resistance value of 1015 at the measurement voltage of 1V, but showed a large decrease to 1010 at the measurement voltage of 10V. On the other hand, Example 1 had a resistance of 10 to the 15th power at a measurement voltage of 1 V, which was higher than that of Comparative Example 1 by two digits. Furthermore, the range of decrease in resistance at a measurement voltage of 10 V was also reduced, and a high resistance of the order of 10 to the 14th power was maintained.
In addition, although Example 2 had a reduced amount of coating carbon black and Example 3 had a reduced amount of photopolymerization initiator as compared with Example 1, both maintained high resistance. From Example 4, high resistance was maintained even when high resistance carbon black with different coating treatment was used.
On the other hand, in Comparative Examples 3 and 4, in which high-resistance carbon black is not used, a large decrease in volume resistivity is observed regardless of the type of photopolymerization initiator.
From the above results, it can be seen that the use of the photopolymerization initiator (c1) as a photopolymerization initiator for a high-resistance black resist can provide a large effect of improving insulation.

Although the detailed mechanism of the effect of the present invention has not been clarified, it is considered as follows.
In conventional high-resistance BM, carbon black that exhibits conductivity is made highly resistant by means of coating, etc., and is further surrounded by a clear component (dispersant, alkali-soluble resin, photopolymerizable monomer, photopolymerization initiator, etc.). As a result, contact between carbon black particles is prevented, and a certain degree of insulation is ensured. It is recognized that this clear component is organic and does not have significant electrical conductivity.
However, when focusing on the photopolymerization initiator among the clear components, the photopolymerization initiator (2) of Comparative Example 1 has a carbazole ring in which three aromatic rings are condensed, resulting in a greatly expanded π orbital. exists. It is believed that this widely spread π orbital serves as a conduction path for electrons, thereby connecting the carbon black particles and facilitating hopping conduction, making it difficult to further increase the resistance. Hopping conduction occurs over the energy barrier existing between conductive molecules, so it is more likely to occur at higher measurement voltages. In particular, it is thought that hopping conduction occurred because the resistivity varied greatly depending on the measured voltage.

On the other hand, the photopolymerization initiator (3) of Comparative Example 2 is advantageous in suppressing hopping conduction derived from the clear component in that the number of condensed aromatic rings is two or less, but it has a diphenyl sulfide skeleton (corresponding to R ^c ) and an oxime ester group (corresponding to --(C=N--O--(CO)--R ^a )--), the sensitivity is rather low. A decrease in sensitivity (a decrease in the degree of cross-linking during exposure) leads to an increase in the fluidity of carbon black particles in the subsequent heat-curing step, making it easier for the carbon black particles to aggregate. It is thought that hopping conduction is likely to occur even when the distance between carbon black particles is narrowed due to aggregation, leading to a decrease in resistance at a measurement voltage of 10V.

On the other hand, in the photopolymerization initiator (1) of Example 1, the benzofuran ring in which two aromatic rings are condensed is the largest aromatic ring, and the spread of the π orbital is small. It is thought that reducing the size of the aromatic (condensed) ring of the photopolymerization initiator leads to an increase in the number of hoppings required for electrical conduction, making it possible to further increase the resistance. Further, it is an oxime ester compound (1) in which a diphenyl sulfide skeleton (corresponding to R ^c ) and an oxime ester group (corresponding to -(C=N-O-(CO)-R ^a )-) are bonded, and sensitivity was high, the flow and agglomeration of the carbon black particles were suppressed in the curing and baking process, and the decrease in resistance at a measurement voltage of 10 V was sufficiently suppressed.
Furthermore, since the photopolymerization initiator (1) has a benzofuran ring, it interacts with carbon black and is easily adsorbed near the particle surface, and passes through the gaps between the high-resistance treatment molecules of the high-resistance carbon black. It is thought that it adsorbs to the surface. As a result, the exposure light is effectively used before it is absorbed by the carbon black, and the curability inside the film is enhanced.
From the above, it can be seen that by using the photosensitive resin composition of the present invention, it is possible to provide a high-resistance black matrix excellent in light-shielding properties and insulating properties.

Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention.

REFERENCE SIGNS LIST 10 transparent support substrate 100 organic EL element 20 pixel 30 organic protective layer 40 inorganic oxide film 50 transparent anode 500 organic light emitter 51 hole injection layer 52 hole transport layer 53 light emitting layer 54 electron injection layer 55 cathode

Claims (8)

A photosensitive resin composition comprising (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, and (d) a colorant,
The (c) photopolymerization initiator contains a photopolymerization initiator (c1) represented by the following general formula (1),
The (d) colorant contains high resistance carbon black (d1),
The high-resistance carbon black (d1) is carbon black subjected to surface coating treatment with a resin, surface coating treatment with a dye, surface oxidation treatment, or surface modification treatment with an organic group having an ionic group,
A photosensitive resin composition , wherein the high resistance carbon black (d1) has a volume resistivity of 3 Ω·cm or more .

(In formula (1) above, R ¹ represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R ² represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R ³ represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R ⁴ represents an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aromatic ring group, a hydroxyl group, or a nitro group; may be bonded via a divalent linking group.
R ⁵ is an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aromatic represents a ring group, a halogen atom, a hydroxyl group, or a 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 formula (1) may contain a condensed ring, but the number of rings contained in the condensed ring is two or less. ) 2. The photosensitive resin composition of claim 1, wherein said high resistance carbon black (d1) comprises coated carbon black. 3. The photosensitive resin composition of claim 2, wherein the coated carbon black is resin-coated carbon black. The photosensitive resin composition according to any one of claims 1 to 3 , wherein the (a) alkali-soluble resin comprises an epoxy (meth)acrylate resin having a carboxyl group. 5. The photosensitive resin composition according to claim 1, which has an optical density of 2.5 or more per 1 μm of film thickness. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 5 . A black matrix comprising the cured product according to claim 6 . An image display device comprising the cured product according to claim 6 .

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