JP7120234B2 - 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, a photosensitive resin composition that has excellent adhesion to a substrate and is capable of suppressing and controlling changes in line width during high-temperature processing and that is suitable for forming high-definition patterns, a cured product obtained by curing the same, and a black matrix; The present invention relates to an image display device having a cured product or the black matrix. The photosensitive resin composition of the present invention is particularly suitable as a photosensitive resin composition for forming a black matrix (hereinafter sometimes abbreviated as "BM") capable of forming fine lines with high sensitivity and high definition. ing.
The full contents of the specification, claims, drawings and abstract of Japanese Patent Application 2017-127704 filed with the Japan Patent Office on June 29, 2017, and documents cited in this specification, etc. A part or all of the content disclosed in is cited here and incorporated as the disclosure content of this 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.

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 nonuniform 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. Since such an increase in the amount of pigment is accompanied by a decrease in the amount of crosslinkable components, it leads to a decrease in adhesion to substrates. Therefore, there is a demand for a countermeasure that does not reduce the adhesion to the substrate.

In Patent Document 1, by using a photosensitive resin composition containing a specific organosilicon compound, good adhesion to substrates can be obtained at room temperature and high temperature and high humidity in the case of high pigment concentration and high fineness. It is stated that it will be
Further, in Patent Document 2, by using a colored curable composition containing a specific compound having an alkoxysilyl group and an acid group, even when the pigment concentration is high, storage stability and curability are excellent, and the substrate and It is described that a colored film having excellent adhesion and developability can be formed.

On the other hand, in order to save energy and prolong the life of mobile batteries, the output of backlights tends to be low. transformation is in progress. In recent years, in the liquid crystal display market, miniaturization such as tablets has become mainstream, and there is an increasing demand for high resolution in large-sized televisions. For these reasons, the demand for higher definition of BM has increased, and in recent years, the line width of BM fine lines has been required to be about 6 μm from the conventional width of about 10 μm.

Japanese Patent Application Laid-Open No. 2016-24319 Japanese Patent Application Laid-Open No. 2010-85723

There is a limit to stably forming a BM thin line pattern with a thickness of about 1 μm and a line width of 6 μm with a forward tapered shape, and a thin line pattern with a taper angle closer to vertical is required. Furthermore, fine line patterns are obtained by curing by high-temperature treatment, but the resin component once softens and flows (melts) before the initiation of the curing reaction, causing a phenomenon in which line widths become thicker. Therefore, there is a demand for a technique for suppressing melting during high-temperature treatment and for controlling the degree of suppression.
The present inventors have studied the photosensitive resin compositions described in Patent Documents 1 and 2, and found that although the adhesion to the substrate is greatly improved, the line width of the thin line is thickened due to melting during high temperature treatment (heat curing). generated, making it difficult to form a fine line pattern.
SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photosensitive resin composition which is excellent in adhesion to substrates and capable of suppressing and controlling line width change during high-temperature processing.

The present inventors have made intensive studies to solve the above problems, and found that the above problems can be solved by including a specific alkali-soluble resin and a specific organosilicon compound in the photosensitive resin composition. That is, the gist of the present invention resides in the following.

[1] A photosensitive resin composition containing (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photoradical polymerization initiator, (d) an organosilicon compound, and (e) a coloring material. hand,
The (a) alkali-soluble resin comprises an epoxy (meth)acrylate resin having a carboxyl group,
A photosensitive resin composition, wherein the organosilicon compound (d) comprises an organosilicon vinyl polymer (d-1) having a repeating unit represented by the following general formula (1).

In formula (1), R ¹ represents a hydrogen atom or an optionally substituted alkyl group,
R ² to R ⁴ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, or represents an aryloxy group which may have a substituent,
L represents a divalent linking group,
x represents 0 or 1;

[2] The photosensitive resin composition according to [1], wherein the (e) colorant contains carbon black.

[3] A cured product obtained by curing the photosensitive resin composition according to [1] or [2].
[4] A black matrix comprising the cured product of [3].
[5] An image display device comprising the cured product of [3] or the black matrix of [4].

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which is excellent in board|substrate adhesion and can suppress and control the line width change at the time of a high temperature process can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is the cross-sectional schematic which shows an example of the organic electroluminescent (organic EL) element provided with the color filter of this 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 polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
Further, 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 weight 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.
In the present invention, the "acid value" is a value measured by the method described in JIS K 2501-2003, unless otherwise specified.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention contains (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photoradical polymerization initiator, (d) an organosilicon compound, and (e) a colorant. In the photosensitive resin composition, the (a) alkali-soluble resin contains an epoxy (meth)acrylate resin having a carboxyl group, and the (d) organosilicon compound is represented by general formula (1) below. It is characterized by containing an organosilicon vinyl polymer (d-1) having a repeating unit.

The photosensitive resin composition of the present invention may further contain dispersants and thiols, and if necessary, other adhesion improvers, surfactants (coatability improvers), pigment derivatives, developing Compounding components such as modifiers, ultraviolet absorbers, antioxidants, etc. 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 characteristics of the present invention is that the photosensitive resin composition contains (d) an organosilicon compound, and in particular, the (d) organosilicon compound contains a repeating unit represented by the general formula (1) described later. The point is that it contains an organosilicon vinyl polymer (d-1). First, (d) the organosilicon compound will be described.

<(d) Organosilicon compound>
The photosensitive resin composition of the present invention contains (d) an organosilicon compound. (d) By containing an organosilicon compound, it becomes possible to bond with a transparent substrate such as glass as a support, and the adhesion to the substrate is improved.

<Organosilicon vinyl polymer (d-1)>
In particular, in the photosensitive resin composition of the present invention, the (d) organosilicon compound is an organosilicon vinyl polymer (d-1) having a repeating unit represented by the following general formula (1) (hereinafter referred to as “organosilicon may be abbreviated as "vinyl polymer (d-1)"). Thus, by containing the organosilicon vinyl polymer (d-1), the organosilicon atom-containing side chains form a large number of cross-linking points through a condensation reaction, resulting in a three-dimensional network structure (cluster) inside the coating film. is considered to form It is believed that the gelation of this three-dimensional network structure suppresses melting. In addition, it is considered that the vinyl polymer blends and spreads in the coating film of the photosensitive resin composition, leading to the formation of uniform clusters.

In formula (1), R ¹ represents a hydrogen atom or an optionally substituted alkyl group,
R ² to R ⁴ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, or represents an aryloxy group which may have a substituent,
L represents a divalent linking group,
x represents 0 or 1;

( ^R1 )
In formula (1) above, R ¹ represents a hydrogen atom or an optionally substituted alkyl group.
The alkyl group may be linear, branched, cyclic, or a combination thereof, and is preferably linear from the viewpoint of the reaction rate during heat curing. Although the number of carbon atoms in the alkyl group is not particularly limited, it is usually 1 or more, preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less. When the content is at least the above lower limit, the solvent solubility tends to be improved, and when the content is at most the above upper limit, the reaction rate during heat curing tends to increase.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, and pentyl group, and methyl group is preferred from the viewpoint of the reaction rate during heat curing.

Examples of substituents that the alkyl group may have include halogen atoms, alkoxy groups, aryl groups, hydroxyl groups, thiol groups, and alkylthio groups. From the viewpoint of storage stability, it is preferably unsubstituted.

( ^R2 - ^R4 )
In the above formula (1), each of R ² to R ⁴ is independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, or a substituted represents an aryl group which may be substituted, or an aryloxy group which may have a substituent.

The alkyl group may be linear, branched, cyclic, or a combination thereof, and is preferably linear from the viewpoint of the reaction rate during heat curing. Although the number of carbon atoms in the alkyl group is not particularly limited, it is usually 1 or more, preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less. When the content is at least the above lower limit, the solvent solubility tends to be improved, and when the content is at most the above upper limit, the reaction rate during heat curing tends to increase.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, and pentyl group, and methyl group is preferred from the viewpoint of the reaction rate during heat curing.

Examples of substituents that the alkyl group may have include halogen atoms, alkoxy groups, aryl groups, hydroxyl groups, thiol groups, and alkylthio groups. From the viewpoint of storage stability, it is preferably unsubstituted.

The alkoxy group may be linear, branched, cyclic, or a combination thereof, and is preferably linear from the viewpoint of the reaction rate during heat curing. Although the number of carbon atoms in the alkyl group is not particularly limited, it is usually 1 or more, preferably 3 or less, and even more preferably 2 or less. When the content is equal to or less than the above upper limit, there is a tendency for the reaction rate during heat curing to increase.

Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, a butoxy group, an i-butoxy group and a pentyloxy group, and a methoxy group is preferred from the viewpoint of the reaction rate during heat curing. .

Examples of substituents that the alkoxy group may have include halogen atoms, alkoxy groups, aryl groups, hydroxyl groups, thiol groups, and alkylthio groups. From the viewpoint of storage stability, it is preferably unsubstituted.

Although the number of rings possessed by the aryl group is not particularly limited, it is generally preferably 1 or more and 4 or less, more preferably 3 or less, and even more preferably 2 or less. When the content is equal to or less than the above upper limit, there is a tendency for the reaction rate during heat curing to increase. Although the number of carbon atoms in the aryl group is not particularly limited, it is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, and preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less. When the content is at least the lower limit, storage stability tends to be improved, and when the content is at most the upper limit, solubility in development tends to be improved.

Aryl groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
Specific examples of the aromatic ring in the aryl group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring. etc. Among these, a benzene ring is preferable from the viewpoint of the reaction rate during heat curing.

Examples of substituents that the aryl group may have include an alkyl group, an alkoxy group, a hydroxyl group, a thiol group, an alkylthio group, and a halogen atom. From the viewpoint of storage stability, it is preferably unsubstituted.

Although the number of rings possessed by the aryloxy group is not particularly limited, it is generally preferably 1 or more and 4 or less, more preferably 3 or less, and still more preferably 2 or less. When the content is equal to or less than the above upper limit, there is a tendency for the reaction rate during heat curing to increase. Although the number of carbon atoms in the aryloxy group is not particularly limited, it is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, and preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less. When the content is at least the lower limit, storage stability tends to be improved, and when the content is at most the upper limit, solubility in development tends to be improved.

The aromatic ring in the aryloxy group includes an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Specific examples of the aromatic ring in the aryloxy group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.
The aryloxy group includes a phenoxy group and a 1-naphthyloxy group. Among these, a phenoxy group is preferable from the viewpoint of the reaction rate during heat curing.

Examples of substituents that the aryloxy group may have include an alkyl group, an alkoxy group, a hydroxyl group, a thiol group, an alkylthio group, and a halogen atom. From the viewpoint of storage stability, it is preferably unsubstituted.

In order to efficiently form a cross-linking point by a condensation reaction, at least one of R ² to R ⁴ may be an alkoxy group which may have a substituent, or may have a substituent. It is preferably a good aryloxy group, more preferably two or more alkoxy groups optionally having substituents, or aryloxy groups optionally having substituents, all of which are substituents or an optionally substituted aryloxy group.
Among these, from the viewpoint of the reaction rate during heat curing, each of R ² to R ⁴ is preferably an optionally substituted alkoxy group, more preferably a methoxy group.

(L)
In formula (1) above, L represents a divalent linking group.
Examples of divalent linking groups include alkylene groups, arylene groups, --CONH-- groups, --CONH--R ⁵ -- groups, --COO-- groups, --COO--R ⁶ -- groups, and combinations thereof. R ⁵ and R ⁶ are each independently an alkylene group, —(CH ₂ CH ₂ O) _Z1 — group (Z1 is an integer of 1 to 100), or —(CH ₂ CH ₂ CH ₂ O) _Z1 — group (Z1 is integer from 1 to 100).

The alkylene group in the divalent linking group may be straight-chain, branched-chain, cyclic, or a combination thereof, and straight-chain is preferred from the viewpoint of the reaction rate during heat curing. Although the number of carbon atoms in the alkylene group is not particularly limited, it is generally preferably 1 or more, 2 or more, more preferably 3 or more, and preferably 16 or less, more preferably 10 or less, and even more preferably 8 or less. Solvent solubility tends to improve by making it more than the said lower limit, and development solubility tends to improve by making it below the said upper limit.

Specific examples of alkylene groups include methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, hexane-1,6-diyl group, methylmethylene group and 1-methylethylene group. and a propane-1,3-diyl group is preferred from the viewpoint of the balance between solvent solubility and development solubility.

Although the number of rings possessed by the arylene group in the divalent linking group is not particularly limited, it is generally preferably 1 or more and 4 or less, more preferably 3 or less, and still more preferably 2 or less. When the content is equal to or less than the above upper limit, there is a tendency that the development solubility is improved. Although the number of carbon atoms in the arylene group is not particularly limited, it is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, and preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less. When the content is at least the lower limit, storage stability tends to be improved, and when the content is at most the upper limit, solubility in development tends to be improved.

Arylene groups include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups.
Specific examples of the aromatic ring in the arylene group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring. etc. Among these, a benzene ring is preferable from the viewpoint of the reaction rate during heat curing.

The alkylene group for R ⁵ and R ⁶ may be linear, branched, cyclic, or a combination thereof, and linear is preferred from the viewpoint of the reaction rate during heat curing. Although the number of carbon atoms in the alkylene group is not particularly limited, it is generally preferably 1 or more, 2 or more, more preferably 3 or more, and preferably 16 or less, more preferably 10 or less, and even more preferably 8 or less. Solvent solubility tends to improve by making it more than the said lower limit, and development solubility tends to improve by making it below the said upper limit.

Specific examples of alkylene groups include methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, hexane-1,6-diyl group, methylmethylene group and 1-methylethylene group. and a propane-1,3-diyl group is preferred from the viewpoint of the balance between solvent solubility and development solubility.

Z1 represents an integer of 1-100. 2 or more is preferable, 4 or more is more preferable, 6 or more is more preferable, 70 or less is preferable, 50 or less is more preferable, 30 or less is more preferable, 15 or less is even more preferable, and 10 or less is particularly preferable. When the amount is at least the lower limit, the solubility in development tends to be improved, and when the amount is at most the upper limit, the formation of development residues tends to be suppressed. The combination of the upper limit and the lower limit is, for example, preferably 2 to 70, more preferably 4 to 50, even more preferably 4 to 30, even more preferably 6 to 15, and particularly preferably 6 to 10.

Among these, from the viewpoint of compatibility with other materials of the photosensitive resin composition, it is preferable that L is a --COO--R ⁶ -- group, and is a --COO--R ⁶ -- group and R ⁶ is more preferably an alkylene group, more preferably a --COO--C ₃ H ₆ -- group.

(x)
In the above formula (1), x represents 0 or 1. Among these, 1 is preferable from the viewpoint of the reaction rate during heat curing.

The content of the repeating unit represented by the general formula (1) contained in the organosilicon vinyl polymer (d-1) is not particularly limited, but is preferably 0.2 mol % or more in all repeating units. mol% or more is more preferable, 10 mol% or more is more preferable, 20 mol% or more is even more preferable, 30 mol% or more is particularly preferable, 40 mol% or more is most preferable, and 100 mol% or less is preferable. mol % or less is more preferable, and 80 mol % or less is even more preferable. When the content is at least the above lower limit, substrate adhesion and the effect of suppressing melting during heat curing tend to increase, and when the content is at most the above upper limit, storage stability tends to improve. As a combination of the upper limit and the lower limit, for example, 0.2 to 100 mol% is preferable, 1 to 90 mol% is more preferable, 10 to 90 mol% is more preferable, 20 to 90 mol% is even more preferable, 30 to 80 mol % is particularly preferred, and 40-80 mol % is most preferred.

From the viewpoint of storage stability, the organosilicon vinyl polymer (d-1) preferably contains a repeating unit represented by the following general formula (2).

In formula (2), R ¹¹ represents a hydrogen atom or an optionally substituted alkyl group.
R ¹² represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group.
M represents a divalent linking group; y represents 0 or 1;

( ^R11 )
In formula (2) above, R ¹¹ represents a hydrogen atom or an optionally substituted alkyl group.
The alkyl group may be linear, branched, cyclic, or a combination thereof, and is preferably linear from the viewpoint of the reaction rate during heat curing. Although the number of carbon atoms in the alkyl group is not particularly limited, it is usually 1 or more, preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less. When the content is at least the above lower limit, the solvent solubility tends to be improved, and when the content is at most the above upper limit, the reaction rate during heat curing tends to increase.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, and pentyl group, and methyl group is preferred from the viewpoint of the reaction rate during heat curing.

Examples of substituents that the alkyl group may have include halogen atoms, alkoxy groups, aryl groups, hydroxyl groups, thiol groups, and alkylthio groups. From the viewpoint of storage stability, it is preferably unsubstituted.

( ^R12 )
In formula (2) above, R ¹² represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group.

The alkyl group may be linear, branched, cyclic, or a combination thereof, and is preferably linear from the viewpoint of the reaction rate during heat curing. Although the number of carbon atoms in the alkyl group is not particularly limited, it is usually 1 or more, preferably 20 or less, more preferably 10 or less, and even more preferably 6 or less. Solvent solubility tends to improve by making it more than the said lower limit, and development solubility tends to improve by making it below the said upper limit.

Specific examples of alkyl groups include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, s-butyl, t-butyl, pentyl, i-pentyl, and neopentyl groups. , t-pentyl group, 2-ethylhexyl group, decyl group, dodecyl group and octadecyl group, and a methyl group is preferred from the viewpoint of the reaction rate during heat curing.

Examples of substituents that the alkyl group may have include halogen atoms, alkoxy groups, aryl groups, hydroxyl groups, thiol groups, and alkylthio groups. From the viewpoint of storage stability, it is preferably unsubstituted.

Although the number of rings possessed by the aryl group is not particularly limited, it is generally preferably 1 or more and 4 or less, more preferably 3 or less, and even more preferably 2 or less. When the content is equal to or less than the above upper limit, there is a tendency that the development solubility is improved. Although the number of carbon atoms in the aryl group is not particularly limited, it is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, and preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less. When the content is at least the lower limit, storage stability tends to be improved, and when the content is at most the upper limit, solubility in development tends to be improved.

Aryl groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
Specific examples of the aromatic ring in the aryl group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring. etc. Among these, a benzene ring is preferable from the viewpoint of the reaction rate during heat curing.

Examples of substituents that the aryl group may have include an alkyl group, an alkoxy group, a hydroxyl group, a thiol group, an alkylthio group, and a halogen atom. From the viewpoint of storage stability, it is preferably unsubstituted.

Among these, an optionally substituted alkyl group is preferred, an unsubstituted alkyl group is more preferred, and a methyl group is even more preferred, from the viewpoint of the reaction rate during heat curing.

(M)
In formula (2) above, M represents a divalent linking group.
Examples of divalent linking groups include alkylene groups, arylene groups, --CONH-- groups, --CONH--R ⁵ -- groups, --COO-- groups, --COO--R ⁶ -- groups, and combinations thereof. R ⁵ and R ⁶ are each independently an alkylene group, —(CH ₂ CH ₂ O) _Z1 — group (Z1 is an integer of 1 to 100), or —(CH ₂ CH ₂ CH ₂ O) _Z1 — group (Z1 is integer from 1 to 100).
As the alkylene group, arylene group, —CONH—R ⁵ —group, —COO—R ⁶ —group, R ⁵ , R ⁶ , and Z1, those mentioned for L in formula (1) can be preferably employed. .
Among these, the -COO- group and the -COO-R ⁶ - group are preferred from the viewpoint of compatibility with other components.
On the other hand, from the viewpoint of development solubility and sensitivity improvement by inhibiting oxygen inhibition, a -COO-(CH ₂ CH ₂ O) _Z1 - group or a -COO-(CH ₂ CH ₂ CH ₂ O) _Z1 - group is preferable. A --COO--(CH ₂ CH ₂ O) _Z1 -- group is more preferred.

(y)
In the above formula (2), y represents 0 or 1. Among these, 1 is preferable from the viewpoint of solvent solubility.

The content of the repeating unit represented by the general formula (2) contained in the organosilicon vinyl polymer (d-1) is not particularly limited, but is preferably 1 mol% or more, more preferably 10 mol% of all repeating units. more preferably 20 mol% or more, more preferably 99.8 mol% or less, more preferably 99 mol% or less, even more preferably 90 mol% or less, even more preferably 80 mol% or less, and 70 mol % or less is particularly preferred, and 60 mol % or less is most preferred. The storage stability tends to be improved by setting it to the above lower limit or more, and the substrate adhesion and the melt suppression effect during heat curing tend to increase by setting it to the above upper limit or less. The combination of the upper limit and the lower limit is, for example, preferably 1 to 99.8 mol%, more preferably 1 to 99 mol%, still more preferably 10 to 90 mol%, even more preferably 10 to 80 mol%, 20 to 70 mol % is particularly preferred, and 20-60 mol % is most preferred.

Further, the organosilicon vinyl polymer (d-1) is a repeating unit represented by the general formula (2), wherein M is a —COO—(CH ₂ CH ₂ O) _Z1 — group. is not particularly limited, but is preferably 1 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more, particularly preferably 20 mol% or more, in all repeating units, and , is preferably 50 mol % or less, more preferably 40 mol % or less, even more preferably 35 mol % or less, and particularly preferably 30 mol % or less. When it is at least the above lower limit, the solubility in development tends to be good, and sensitivity tends to improve due to inhibition of oxygen inhibition. tend to rise. The combination of the upper limit and the lower limit is, for example, preferably 1 to 50 mol%, more preferably 10 to 40 mol%, even more preferably 15 to 35 mol%, and particularly preferably 20 to 30 mol%.

The weight average molecular weight (Mw) of the organosilicon vinyl polymer (d-1) is not particularly limited, but is preferably 2,000 or more, more preferably 5,000 or more, still more preferably 8,000 or more, and preferably 100,000 or less, and 75,000 or less. It is more preferably 40,000 or less, even more preferably 30,000 or less, and particularly preferably 20,000 or less. When the content is equal to or higher than the lower limit, the effect of suppressing melt tends to increase, and when the content is equal to or lower than the upper limit, solubility in development tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 2,000 to 100,000, more preferably 5,000 to 75,000, even more preferably 5,000 to 40,000, even more preferably 8,000 to 30,000, and particularly preferably 8,000 to 20,000.

The acid value of the organosilicon vinyl polymer (d-1) is not particularly limited, but is preferably 3 mgKOH/g or less, more preferably 1 mgKOH/g or less, still more preferably 0.5 mgKOH/g or less, and 0.3 mgKOH/g or less. is particularly preferred and 0 mg KOH/g is most preferred. When the content is equal to or less than the above upper limit, the storage stability of the organosilicon vinyl polymer (d-1) tends to be improved.

Although the method for producing the organosilicon vinyl polymer (d-1) is not particularly limited, it can be obtained, for example, by copolymerizing a silicon atom-containing unsaturated compound with another unsaturated compound.

Silicon atom-containing unsaturated compounds include, for example, compounds as exemplified below. These may be used individually by 1 type, and may be used in arbitrary combinations and ratios of 2 or more types.
In the formula, C ₂ H ₄ is a 1,2-ethylene group, C ₃ H ₆ is an n-propane-1,3-diyl group, and C ₈ H ₁₆ is an n-octane-1,8-diyl group. represents

Other unsaturated compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isoamyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate ) acrylate, 2-ethylhexyl diglycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate ) acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, trifluoroethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate Acrylates are mentioned. These may be used individually by 1 type, and may be used in arbitrary combinations and ratios of 2 or more types. From the viewpoint of the storage stability of the organosilicon vinyl (d-1), it is preferable to copolymerize using an unsaturated compound that does not have an acidic group.

Although the content of (d) the organosilicon compound in the photosensitive resin composition of the present invention is not particularly limited, it is preferably 0.1% by mass or more, and 0.3% by mass or more, based on the total solid content of the photosensitive resin composition. is more preferable, 1% by mass or more is more preferable, 2% by mass or more is particularly preferable, 15% by mass or less is preferable, 10% by mass or less is more preferable, 8% by mass or less is more preferable, and 5% by mass or less is Especially preferred. When the content is at least the above lower limit, there is a tendency for substrate adhesion to improve, and when the content is at most the above upper limit, there is a tendency for development residue to be suppressed. A combination of the upper limit and the lower limit is, for example, preferably 0.1 to 15% by mass, more preferably 0.3 to 10% by mass, still more preferably 1 to 8% by mass, and particularly preferably 2 to 5% by mass.

The content of the organosilicon vinyl polymer (d-1) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.1% by mass or more based on the total solid content of the photosensitive resin composition, and 0.1% by mass or more. 3% by mass or more is more preferable, 1% by mass or more is more preferable, 1.5% by mass or more is even more preferable, 2% by mass or more is particularly preferable, and 10% by mass or less is preferable, and 8% by mass or less is more preferable. Preferably, 5% by mass or less is more preferable. When the content is at least the above lower limit, the effect of suppressing melting during heat curing tends to increase, and when the content is at most the above upper limit, development residues tend to be suppressed. The combination of the upper limit and the lower limit is, for example, preferably 0.1 to 10% by mass, more preferably 0.3 to 10% by mass, even more preferably 1 to 8% by mass, and even more preferably 1.5 to 5% by mass. 2 to 5% by weight is particularly preferred.
Two or more of the organosilicon vinyl polymer (d-1) may be used in any combination and ratio.

<Other organosilicon compounds (d-2)>
In addition to the organosilicon vinyl polymer (d-1), the organosilicon compound (d) may contain another organosilicon compound (d-2).
Other organosilicon compounds include silane coupling agents, such as vinyl groups, epoxy groups, styryl groups, methacrylic groups, acrylic groups, primary to tertiary amino groups, ureido groups, and mercapto groups, such as the following: , isocyanate groups 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.
In the formula, C ₂ H ₄ represents a 1,2-ethylene group, and C ₃ H ₆ represents an n-propane-1,3-diyl group.

<(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 cured film obtained by coating and drying the photosensitive resin composition is changed in solubility in alkali development between the exposed area and the non-exposed area after exposure. However, it is preferably an alkali-soluble resin having a carboxyl group. From the viewpoint of photocurability, those having ethylenically unsaturated groups are preferable, and from the viewpoint of photocurability and development solubility, alkali-soluble resins having ethylenically unsaturated groups and carboxyl groups are more preferable. Specific examples include epoxy (meth)acrylate resins and acrylic copolymer resins having carboxyl groups.

When making a color filter, since the non-exposed areas are usually dissolved in alkaline developer, 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. Applies. 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.

The (a) alkali-soluble resin in the photosensitive resin composition of the present invention contains an epoxy (meth)acrylate resin having a carboxyl group. Epoxy (meth)acrylate resins having carboxyl groups have ethylenically unsaturated groups, which increase the number of cross-linking points during exposure, raise the softening start temperature, and suppress line width changes due to resin flow. It is considered to be a thing. Epoxy (meth)acrylate resins with carboxyl groups also have π-π interactions between aromatic rings in addition to hydrogen bonding and dipole-dipole interactions due to carboxyl groups and ester groups. Since the free volume between chains is reduced and oxygen is less permeable, it is thought that inhibition of oxygen during the polymerization reaction is suppressed, cross-linking proceeds further, and line width change due to resin flow is suppressed.

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 resulting hydroxyl group. 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 is reacted. A resin obtained by reaction is also included in the epoxy (meth)acrylate resin. 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 having a carboxyl group has substantially no epoxy group in terms of chemical structure, and is not limited to "(meth)acrylate", but epoxy resin is a raw material. and "(meth)acrylate" is a typical example, so it is named in this way according to common practice.

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 of 0 to 10, R ¹¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms , represents 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 above general formula (a2), b12 is an average value and represents a number of 0 to 10, R ²¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms , represents 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, and b13 represents an integer of 2 or 3. However, it contains one or more adamantane structures in its molecular structure.

In general formulas (a3-1) and (a3-2) above, R ³¹ to R ³⁴ and R ³⁵ to R ³⁷ each independently represent an optionally substituted adamantyl group, a hydrogen atom, or a substituent. represents an optionally substituted alkyl group having 1 to 12 carbon atoms or a phenyl group which may have a substituent, and * in the formula represents a bonding site in the general formula (a3).

In the general formula (a4), p and q each independently represent an integer of 0 to 4, R ⁴¹ and R ⁴² each independently represent an alkyl group or a halogen atom, R ⁴³ and R ⁴⁴ each independently represent an alkylene group, and 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. R ⁵⁵ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, R ⁵⁶ represents an alkylene group having 1 to 5 carbon atoms, and k represents an integer of 1 to 5, l represents an integer of 0 to 13, and m represents an integer of 0 to 5.
Among these, epoxy resins represented by any one of general formulas (a1) to (a5) are preferably used.

Examples of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having a carboxyl group include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, (meth) ) Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted acrylic acid, 2-(meth) acryloyloxyethyl succinic acid, 2-(meth) acryloyloxyethyl adipic 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-(meth) Acryloyloxybutyl maleic acid, (meth)acrylic acid to which lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone and δ-valerolactone are added and monomers having one hydroxyl group at the end; , Alternatively, a monomer having one hydroxyl group at the end such as hydroxyalkyl (meth) acrylate, or a compound having one hydroxyl group at the end such as pentaerythritol tri (meth) acrylate, (anhydrous) succinic acid , (anhydrous) phthalic acid, (anhydride) by adding an acid (anhydride) such as maleic acid (meth)acrylic acid ester having one or more ethylenically unsaturated groups and one carboxyl group at the end, etc. be done. (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 and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used alone, You may use 2 or more types together.
The amount of the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group is in the range of 0.5 to 1.2 equivalents per equivalent of the epoxy group of the epoxy resin. is preferred, more preferably in the range of 0.7 to 1.1 equivalents.
When the amount of the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group is at least the above lower limit, the amount of the unsaturated group introduced becomes sufficient, and the subsequent polybasic acid and/or reaction with its anhydride also tends to be sufficient. On the other hand, when the amount is not more than the upper limit, there is a tendency 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. .

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)>
Polyhydric alcohols 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. 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 its anhydride 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 .

The amount of the polyhydric alcohol to be used is usually 0.01 to 0.01 to the reaction product of the epoxy resin and the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group. It is about 0.5 times by mass, preferably about 0.02 to 0.2 times by mass. When the content is equal to or higher than the lower limit, the effect of addition tends to be easily obtained, and when the content is equal to or lower than the upper limit, thickening and gelation tend to be suppressed.

In the photosensitive resin composition of the present invention, from the viewpoint of surface curability, the epoxy (meth)acrylate resin (A1 -1) and (A1-2) are preferably included.

Epoxy (meth)acrylate resins having a carboxyl group may be used singly or as a mixture of two or more resins.
Although the acid value of the epoxy (meth)acrylate resin having a carboxyl group is not particularly limited, it is usually 10 mgKOH/g or more, preferably 50 mgKOH/g or more, more preferably 80 mgKOH/g or more, and 200 mgKOH/g or less. It is preferably 150 mgKOH/g or less, more preferably 130 mgKOH/g or less. 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, for example, preferably 10 to 200 mgKOH/g, more preferably 50 to 150 mgKOH/g, and even more preferably 80 to 130 mgKOH/g.

The polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the epoxy (meth)acrylate resin having a carboxyl group is not particularly limited, but is preferably 1000 or more, and preferably 1500 or more. More preferably, it is 2000 or more. Also, it is preferably 40,000 or less, more preferably 20,000 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, for example, preferably 1000 to 40000, more preferably 1500 to 20000, even more preferably 1500 to 10000, even more preferably 2000 to 8000, and particularly preferably 2000 to 6000.

The chemical structure of the epoxy (meth)acrylate resin having a carboxyl group is not particularly limited, but from the viewpoint of exposure sensitivity, an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (a1-I) (hereinafter referred to as Sometimes abbreviated as "(a1-I) epoxy (meth)acrylate resin".) and / or epoxy (meth)acrylate resin having a partial structure represented by the following general formula (a1-II) (hereinafter, " (a1-II) may be abbreviated as "epoxy (meth)acrylate resin").

In formula (a1-I), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents an optionally substituted divalent hydrocarbon group, and * represents a bond. The benzene ring in formula (a1-I) may be further substituted with any substituent.

In formula (a1-II), R ¹³ each independently represents a hydrogen atom or a methyl group, R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, R ¹⁵ and R ¹⁶ each independently represents a divalent aliphatic group which may have a substituent, m and n each independently represent an integer of 0 to 2, and * represents a bond.

<(a1-I) epoxy (meth)acrylate resin>
First, the epoxy (meth)acrylate resin having the partial structure represented by the general formula (a1-I) will be described in detail.

In formula (a1-I), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents an optionally substituted divalent hydrocarbon group, and * represents a bond. The benzene ring in formula (a1-I) may be further substituted with any substituent.

( ^R12 )
In formula (a1-I) above, R ¹² represents a divalent hydrocarbon group which may have a substituent.
The divalent hydrocarbon group includes a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked. mentioned.

The divalent aliphatic group includes linear, branched, cyclic, and combinations thereof. Among these, linear ones are preferred from the viewpoint of developing solubility. On the other hand, from the viewpoint of reducing permeation of the developing solution into the exposed area, an annular shape is preferable. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the content is at least the lower limit, a strong film tends to be easily obtained, and when the content is at most the upper limit, the resolution tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 1-20, more preferably 3-15, and even more preferably 6-10.

Specific examples of divalent linear aliphatic groups include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group and the like. . Among these, a methylene group is preferable from the viewpoint of rigidity of the skeleton.
The divalent branched aliphatic group includes the divalent linear aliphatic group described above, and a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group as a side chain. , an iso-butyl group, a sec-butyl group, a tert-butyl group, and the like.
Although the number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. When the content is at least the lower limit, the film tends to be strong, and when the content is at most the upper limit, the resolution tends to be improved. Specific examples of divalent cyclic aliphatic groups include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, dicyclopentadiene ring, etc., from which two hydrogen atoms are removed. The group which carried out is mentioned. Among these, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable from the viewpoint of rigidity of the skeleton.

Substituents which the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxyl group. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

Moreover, a bivalent aromatic-hydrocarbon ring group and a bivalent aromatic heterocyclic group are mentioned as a bivalent aromatic ring group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the content is at least the lower limit, a strong film tends to be easily obtained, and when the content is at most the upper limit, the resolution tends to be improved. A combination of the upper limit and the lower limit is, for example, preferably 4 to 20, more preferably 5 to 15, and even more preferably 6 to 10.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. The aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, which have two free valences, Groups such as acenaphthene ring, fluoranthene ring, and fluorene ring can be mentioned.
Moreover, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring and carbazole ring having two free valences. ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, Groups such as pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
Among these, from the viewpoint of resolution, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

Examples of substituents that the divalent aromatic ring group may have include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. Among these, non-substitution is preferred from the viewpoint of resolution.

Further, as the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic Groups in which one or more cyclic groups are linked can be mentioned.
Although the number of divalent aliphatic groups is not particularly limited, it is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, polymerization tends to proceed easily, and when the content is equal to or lower than the upper limit, resolution tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.
Although the number of divalent aromatic ring groups is not particularly limited, it is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is at least the lower limit, a strong film tends to be easily obtained, and when the content is at most the upper limit, the resolution tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.

Specific examples of groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include the following formulas (a1-IA) to (a1-IF). and the like. Among these, a group represented by the following formula (a1-IA) is preferable from the viewpoint of resolution.

As described above, the benzene ring in formula (a1-I) may be further substituted with optional substituents. Examples of the substituent include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. The number of substituents is also not particularly limited, and may be one or two or more.
Among these, non-substitution is preferred from the viewpoint of resolution.

Further, the partial structure represented by the above formula (a1-I) is preferably a partial structure represented by the following formula (a1-I-1) from the viewpoint of ease of synthesis.

In formula (a1-I-1), R ¹¹ and R ¹² have the same definitions as in formula (a1-I) above, R represents a hydrogen atom or a ^polybasic acid residue, and * represents a bond. show. The benzene ring in formula (a1-I-1) may be further substituted with any substituent.

A polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetrahydrophthalic acid. One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be used.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties, and more preferred. are tetrahydrophthalic acid, pyromellitic acid, biphenyltetracarboxylic acid.

(a1-I) The partial structure represented by the formula (a1-I-1) contained in one molecule of the epoxy ( ^meth )acrylate resin may be one or two or more. Atoms and those in which R ^X is a polybasic acid residue may be mixed.

In addition, the number of partial structures represented by the formula (a1-I) contained in one molecule of the (a1-I) epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. It is preferably 20 or less, more preferably 15 or less. When the content is at least the lower limit, the solubility in development tends to increase, and when the content is at most the upper limit, the resolution tends to improve. The combination of the upper limit and the lower limit is, for example, preferably 1-20, more preferably 3-15.

(a1-I) epoxy (meth)acrylate resin, the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is not particularly limited, preferably 1000 or more, more preferably 1500 or more, 2000 or more is more preferable, 2500 or more is more preferable, 3000 or more is particularly preferable, 3500 or more is most preferable, and 30000 or less is preferable, 20000 or less is more preferable, 10000 or less is more preferable, and 9000 or less is even more preferable. , 8000 or less is particularly preferred, and 7000 or less is most preferred. When the content is at least the lower limit, the resolution tends to be good, and when the content is at most the upper limit, the re-solubility tends to be good. The combination of the upper limit and the lower limit is, for example, preferably 1000 to 30000, more preferably 1500 to 20000, more preferably 2000 to 10000, even more preferably 2500 to 9000, particularly preferably 3000 to 8000, most preferably 3500 to 7000. It is preferably mentioned.

The acid value of (a1-I) the epoxy (meth)acrylate resin is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, still more preferably 40 mgKOH/g or more, and more preferably 50 mgKOH/g or more. It is more preferably 80 mgKOH/g or more, particularly preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, even more preferably 130 mgKOH/g or less, and particularly preferably 120 mgKOH/g or less. When it is set to the above lower limit or more, the solubility in development tends to be improved and the resolution tends to be improved. There is The combination of the upper limit and the lower limit is, for example, preferably 10 to 200 mgKOH/g, more preferably 20 to 150 mgKOH/g, still more preferably 40 to 150 mgKOH/g, even more preferably 50 to 130 mgKOH/g, and even more preferably 80 to 120 mgKOH/g. g is particularly preferred.

Specific examples of the (a1-I) epoxy (meth)acrylate resin are given below. Note that * in the examples indicates a bond.

<(a1-II) epoxy (meth)acrylate resin>
Next, the epoxy (meth)acrylate resin having the partial structure represented by the general formula (a1-II) will be described in detail.

In formula (a1-II), R ¹³ each independently represents a hydrogen atom or a methyl group, R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, R ¹⁵ and R ¹⁶ each independently represents a divalent aliphatic group which may have a substituent, m and n each independently represent an integer of 0 to 2, and * represents a bond.

( ^R14 )
In general formula (a1-II), R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.

Although the number of rings possessed by the aliphatic ring group is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is at least the lower limit, a strong film tends to be easily obtained, and when the content is at most the upper limit, the resolution tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.
The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly 15 or less. preferable. When the content is at least the lower limit, a strong film tends to be easily obtained, and when the content is at most the upper limit, the resolution tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 4-40, more preferably 6-30, and even more preferably 8-20.
Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring and adamantane ring. Among these, an adamantane ring is preferable from the viewpoint of the residual film ratio and resolution of the photosensitive resin composition.

On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, and 4 or less. is more preferred. When the content is at least the lower limit, a strong film tends to be easily obtained, and when the content is at most the upper limit, the resolution tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 1 to 10, more preferably 2 to 5, and even more preferably 3 to 4.
Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, and 30 or less. It is more preferably 20 or less, and particularly preferably 15 or less. When the content is at least the lower limit, the resolution tends to be good, and when the content is at most the upper limit, the re-solubility tends to be good. A combination of the upper limit and the lower limit is, for example, preferably 4 to 40, more preferably 6 to 30, still more preferably 8 to 20, and particularly preferably 10 to 15.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, A fluorene ring and the like can be mentioned. Among these, a fluorene ring is preferable from the viewpoint of developing solubility.

In addition, the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited. and a group in which a divalent aliphatic group and one or more divalent aromatic ring groups are linked.

Divalent aliphatic groups include linear, branched, cyclic, and combinations thereof. Among these, linear ones are preferable from the viewpoint of developing solubility, while cyclic ones are preferable from the viewpoint of reducing permeation of the developer into the exposed area. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less. When the content is at least the lower limit, a strong film tends to be easily obtained, and when the content is at most the upper limit, the resolution tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 1 to 25, more preferably 3 to 20, and even more preferably 6 to 15.

Specific examples of divalent linear aliphatic groups include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group and the like. . Among these, a methylene group is preferable from the viewpoint of resolution.
The divalent branched aliphatic group includes the divalent linear aliphatic group described above, and a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group as a side chain. , an iso-butyl group, a sec-butyl group, a tert-butyl group, and the like.
Although the number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is at least the lower limit, the film tends to be strong, and when the content is at most the upper limit, the resolution tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.
Specific examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a ring such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring and adamantane ring. be done. Among these, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable from the viewpoint of the residual film ratio and resolution of the photosensitive resin composition.

Substituents which the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxyl group. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

Moreover, a bivalent aromatic-hydrocarbon ring group and a bivalent aromatic heterocyclic group are mentioned as a bivalent aromatic ring group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. When the content is at least the lower limit, a strong film tends to be easily obtained, and when the content is at most the upper limit, the resolution tends to be improved. A combination of the upper limit and the lower limit is, for example, preferably 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. The aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, which have two free valences, Groups such as acenaphthene ring, fluoranthene ring, and fluorene ring can be mentioned.
Moreover, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring and carbazole ring having two free valences. ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, Groups such as pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. Among these, from the viewpoint of resolution, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

Examples of substituents that the divalent aromatic ring group may have include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. Among these, non-substitution is preferred from the viewpoint of resolution.

Further, as the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic Groups in which one or more cyclic groups are linked can be mentioned.
Although the number of divalent aliphatic groups is not particularly limited, it is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is at least the lower limit, a strong film tends to be easily obtained, and when the content is at most the upper limit, the resolution tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.
Although the number of divalent aromatic ring groups is not particularly limited, it is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is at least the lower limit, a strong film tends to be easily obtained, and when the content is at most the upper limit, the resolution tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.

Specific examples of groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include the above formulas (a1-IA) to (a1-IF). and the like. Among these, the group represented by the above formula (a1-IC) is preferable from the viewpoint of resolution.

The bonding mode of the side chain cyclic hydrocarbon group to these divalent hydrocarbon groups is not particularly limited, but for example, one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with the side chain. and a mode in which a cyclic hydrocarbon group, which is a side chain, is formed including one of the carbon atoms of the aliphatic group.

⁽ R15, ^R16 )
In the general formula (a1-II), R ¹⁵ and R ¹⁶ each independently represent a divalent aliphatic group which may have a substituent.

Divalent aliphatic groups include linear, branched, cyclic, and combinations thereof. Among these, a linear one is preferred from the viewpoint of development solubility, while a cyclic one is preferred from the viewpoint of the residual film ratio and resolution of the photosensitive resin composition. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the content is at least the lower limit, a strong film tends to be easily obtained, and when the content is at most the upper limit, the resolution tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 1-20, more preferably 3-15, and even more preferably 6-10.

Specific examples of divalent linear aliphatic groups include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group and the like. . Among these, a methylene group is preferable from the viewpoint of resolution.
The divalent branched aliphatic group includes the divalent linear aliphatic group described above, and a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group as a side chain. , an iso-butyl group, a sec-butyl group, a tert-butyl group, and the like.
Although the number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. When the content is at least the lower limit, the film tends to be strong, and when the content is at most the upper limit, the resolution tends to be improved. As a combination of the upper limit and the lower limit, for example, 1 to 12 are preferable, and 2 to 10 are more preferable.
Specific examples of divalent cyclic aliphatic groups include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, dicyclopentadiene ring, etc., from which two hydrogen atoms are removed. The group which carried out is mentioned. Among these, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable from the viewpoint of rigidity of the skeleton.

Substituents which the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxyl group. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

(m,n)
In the general formula (a1-II), m and n each independently represent an integer of 0-2. When the content is at least the lower limit, the surface curability tends to be good, and when the content is at most the upper limit, the resolution tends to be good. From the standpoint of developability, m and n are preferably 0. On the other hand, m and n are preferably 1 or more from the viewpoint of the residual film ratio.

Further, the partial structure represented by the general formula (a1-II) is preferably a partial structure represented by the following general formula (a1-II-1) from the viewpoint of affinity with the coloring material.

In formula (a1-II-1), R ¹³ , R ¹⁵ , R ¹⁶ , m and n are as defined in formula (a1-II) above, and R ^α is a monovalent optionally substituted represents a cyclic hydrocarbon group, p is an integer of 1 or more, and * represents a bond. The benzene ring in formula (a1-II-1) may be further substituted with any substituent.

(R ^α )
In general formula (a1-II-1) above, R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.

Although the number of rings possessed by the aliphatic ring group is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, a strong film tends to be easily obtained, and when the content is equal to or lower than the upper limit, the resolution tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 1 to 6, more preferably 2 to 4, and even more preferably 2 to 3.
The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly 15 or less. preferable. When the content is equal to or higher than the lower limit, a strong film tends to be easily obtained, and when the content is equal to or lower than the upper limit, the resolution tends to be improved. A combination of the upper limit and the lower limit is, for example, preferably 4 to 40, more preferably 6 to 30, still more preferably 8 to 20, and particularly preferably 8 to 15.
Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring and adamantane ring. Among these, an adamantane ring is preferable from the viewpoint of strong film properties.

On the other hand, although the number of rings possessed by the aromatic ring group is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, a strong film tends to be easily obtained, and when the content is equal to or lower than the upper limit, the resolution tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. When the content is equal to or higher than the lower limit, a strong film tends to be easily obtained, and when the content is equal to or lower than the upper limit, the resolution tends to be improved. A combination of the upper limit and the lower limit is, for example, preferably 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like. Among these, a fluorene ring is preferable from the viewpoint of pigment affinity.

Examples of substituents that the cyclic hydrocarbon group may have include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Alkyl groups having 1 to 5 carbon atoms such as iso-amyl groups; alkoxy groups having 1 to 5 carbon atoms such as methoxy groups and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; Among these, unsubstituted is preferred from the viewpoint of ease of synthesis.

p represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. When the content is equal to or higher than the lower limit, a strong film tends to be easily obtained, and when the content is equal to or lower than the upper limit, the resolution tends to be improved. As a combination of the upper limit and the lower limit, for example, 1 to 3 are preferable, and 2 to 3 are more preferable.

Among these, from the viewpoint of resolution, R ^α is preferably a monovalent aliphatic cyclic group, more preferably an adamantyl group.

As described above, the benzene ring in formula (a1-II-1) may be further substituted with any substituent. Examples of the substituent include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. The number of substituents is also not particularly limited, and may be one or two or more.
Among these, non-substitution is preferred from the viewpoint of patterning properties.

Specific examples of the partial structure represented by the formula (a1-II-1) are shown below.

Further, the partial structure represented by the general formula (a1-II) is a partial structure represented by the following general formula (a1-II-2) from the viewpoint of affinity with the coloring material and developability. is preferred.

In formula (a1-II-2), R ¹³ , R ¹⁵ , R ¹⁶ , m and n are the same as defined in formula (a1-II) above, and R ^β is a divalent optionally substituted represents a cyclic hydrocarbon group, and * represents a bond. The benzene ring in formula (a1-II-2) may be further substituted with any substituent.

( ^Rβ )
In the above formula (a1-II-2), R ^β represents a divalent cyclic hydrocarbon group which may have a substituent.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.

Although the number of rings possessed by the aliphatic ring group is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the content is at least the lower limit, a strong film tends to be easily obtained, and when the content is at most the upper limit, the resolution tends to be improved. As a combination of the upper limit and the lower limit, for example, 1 to 10 are preferable, and 1 to 5 are more preferable.
In addition, the number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, further preferably 8 or more, preferably 40 or less, more preferably 35 or less, and further preferably 30 or less. preferable. When the content is at least the lower limit, a strong film tends to be easily obtained, and when the content is at most the upper limit, the resolution tends to be improved. A combination of the upper limit and the lower limit is, for example, preferably 4 to 40, more preferably 5 to 35, and even more preferably 6 to 30.
Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of film retention rate and resolution.

On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. When the content is at least the lower limit, a strong film tends to be easily obtained, and when the content is at most the upper limit, the resolution tends to be improved. A combination of the upper limit and the lower limit is, for example, preferably 1 to 10, more preferably 2 to 5, and even more preferably 3 to 5.
Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. In addition, the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, preferably 40 or less, more preferably 30 or less, and further preferably 20 or less. It is preferred, and 15 or less is particularly preferred. When the content is at least the lower limit, a strong film tends to be easily obtained, and when the content is at most the upper limit, the resolution tends to be improved. A combination of the upper limit and the lower limit is, for example, preferably 4 to 40, more preferably 6 to 30, still more preferably 8 to 20, and particularly preferably 8 to 15.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, indane ring, fluorene ring and the like. Among these, from the viewpoint of developability, an indane ring or a fluorene ring is preferable, and a fluorene ring is more preferable.

Examples of substituents that the cyclic hydrocarbon group may have include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Alkyl groups having 1 to 5 carbon atoms such as iso-amyl groups; alkoxy groups having 1 to 5 carbon atoms such as methoxy groups and ethoxy groups; phenyl groups; hydroxyl groups; nitro groups; Among these, non-substituted groups are preferred from the viewpoint of ease of synthesis.

Among these, R ^β is preferably a divalent aliphatic cyclic group, more preferably a divalent adamantane cyclic group, from the viewpoint of film retention rate and resolution.
On the other hand, from the viewpoint of developability, R ^β is preferably a divalent aromatic ring group, more preferably a divalent fluorene ring group or a divalent phenylindane ring group.

As described above, the benzene ring in formula (a1-II-2) may be further substituted with any substituent. Examples of the substituent include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. The number of substituents is also not particularly limited, and may be one or two or more.
Moreover, two benzene rings may be connected via a substituent. Substituents in this case include divalent groups such as —O—, —S—, —NH—, and —CH ₂ —.
Among these, non-substitution is preferred from the viewpoint of resolution. Moreover, from the viewpoint of making it difficult to cause film reduction, etc., substitution with a methyl group is preferred.

Specific examples of the partial structure represented by the formula (a1-II-2) are shown below. Note that * in the examples indicates a bond.

On the other hand, the partial structure represented by the formula (a1-II) is preferably a partial structure represented by the following formula (a1-II-3) from the viewpoint of film retention and resolution.

In formula (a1-II-3), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , m and n are the same as defined in formula (a1-II) above, and R ^Z is a hydrogen atom or a polybasic acid residue. show.

A polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. In addition, one more OH group may be removed and shared with R ^Z in another molecule represented by formula (a1-II-3), that is, multiple ^groups of formula (a1 -II-3) may be linked.
Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetrahydrophthalic acid. One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be mentioned.
Among these, from the viewpoint of resolution, the polybasic acid is preferably maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetra Carboxylic acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid, biphenyltetracarboxylic acid.

(a1-II) The partial structure represented by the formula (a1-II-3) contained in one molecule of the epoxy ( ^meth )acrylate resin may be one or two or more. Atoms and those in which R ^Z is a polybasic acid residue may be mixed.

In addition, the number of partial structures represented by the formula (a1-II) contained in one molecule of the (a1-II) epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. It is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the content is at least the lower limit, a strong film tends to be easily obtained, and when the content is at most the upper limit, the resolution tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 1-20, more preferably 3-15, and even more preferably 3-10.

(a1-II) The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more. Also, it is preferably 30,000 or less, more preferably 20,000 or less, even more preferably 10,000 or less, even more preferably 7,000 or less, and particularly preferably 6,000 or less. When the amount is at least the lower limit, the developability tends to be good, and when the amount is at most the upper limit, the re-solubility tends to be good. The combination of the upper limit and the lower limit is, for example, preferably 1,000 to 30,000, more preferably 1,000 to 20,000, even more preferably 2,000 to 10,000, even more preferably 2,000 to 7,000, and particularly preferably 2,000 to 6,000.

(a1-II) The acid value of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, still more preferably 40 mgKOH/g or more, and even more preferably 60 mgKOH/g or more. It is preferably 80 mgKOH/g or more, most preferably 90 mgKOH/g or more, preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, and even more preferably 120 mgKOH/g or less. When the content is at least the above lower limit, the solubility of the uncured portion in development tends to increase, and when the content is at most the above upper limit, the resolution tends to be good. The combination of the upper limit and the lower limit is, for example, preferably 10 to 200 mgKOH/g, more preferably 20 to 150 mgKOH/g, still more preferably 40 to 150 mgKOH/g, even more preferably 60 to 120 mgKOH/g, and even more preferably 80 to 120 mgKOH/g. g is particularly preferred.

The (a) alkali-soluble resin in the photosensitive resin composition of the present invention contains an epoxy (meth)acrylate resin having a carboxyl group, but may further contain other alkali-soluble resins. Other alkali-soluble resins include, for example, acrylic copolymer resins.

Examples of acrylic copolymer resins include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11. -174224, JP-A-2000-56118, JP-A-2003-233179, JP-A-2007-270147, etc. Various polymer compounds described in each publication can be used. However, the following resins (A2-1) to (A2-4) are preferred, among which the 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): A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (A2-2) (A2-4): (meth)acrylic resin

From the viewpoint of sensitivity and melt suppression, the photosensitive resin composition of the present invention preferably contains an ethylenically unsaturated group-containing alkali-soluble resin. As the alkali-soluble resin containing an ethylenically unsaturated group, in addition to the aforementioned epoxy (meth)acrylate resin having a carboxyl group, at least one of the resin (A2-1) and the resin (A2-3). preferably included.

In the photosensitive resin composition of the present invention, an alkali-soluble resin other than the acrylic copolymer resin may be used in combination as another alkali-soluble resin. When an alkali-soluble resin other than the acrylic copolymer resin is used in combination as another alkali-soluble resin, it 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, and still more preferably 20% by mass or more in the total solid of the photosensitive resin composition. and is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, and still more preferably 30% 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 of images and good adhesion. A combination of the upper limit and the lower limit is, for example, preferably 5 to 90% by mass, more preferably 10 to 70% by mass, still more preferably 15 to 50% by mass, and particularly preferably 20 to 30% by mass.

In addition, the content of the epoxy (meth)acrylate resin having a carboxyl group is not particularly limited, but usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass in the total solid of the photosensitive resin composition. % or more, more preferably 20 mass % or more, and usually 90 mass % or less, preferably 70 mass % or less, more preferably 50 mass % or less, still more preferably 30 mass % or less. When the content is at least the above lower limit, development residue tends to be suppressed, and when the content is at most the above upper limit, the resolution tends to be good. A combination of the upper limit and the lower limit is, for example, preferably 5 to 90% by mass, more preferably 10 to 70% by mass, still more preferably 15 to 50% by mass, and particularly preferably 20 to 30% by mass.

In addition, the content of the epoxy (meth)acrylate resin having a carboxyl group in (a) the alkali-soluble resin is not particularly limited, but it is preferably 20% by mass or more, and 40% by mass or more in the (a) alkali-soluble resin. is more preferably 60% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, most preferably 95% by mass or more, and usually 100% by mass or less. When the content is equal to or higher than the lower limit, the resolution tends to be good. The combination of the upper limit and the lower limit is, for example, preferably 20 to 100% by mass, more preferably 40 to 100% by mass, even more preferably 60 to 100% by mass, even more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass. % is particularly preferred, and 95-100% by weight is most preferred.

As described above, in the photosensitive resin composition of the present invention, when the (a) alkali-soluble resin contains another alkali-soluble resin, the content ratio thereof is not particularly limited. On the other hand, it is usually 20% by mass or less, preferably 10% by mass or less, and particularly preferably 0% by mass.

The content ratio of (a) alkali-soluble resin to 100 parts by mass of (b) photopolymerizable monomer is not particularly limited, but is preferably 100 parts by mass or more, more preferably 130 parts by mass or more, and further preferably 160 parts by mass or more. , 200 parts by mass or more is particularly preferable, 2000 parts by mass or less is preferable, 1500 parts by mass or less is more preferable, 1000 parts by mass or less is even more preferable, and 500 parts by mass or less is particularly preferable. When the concentration is equal to or higher than the lower limit, the development residue tends to be suppressed, and when the concentration is equal to or lower than the upper limit, the exposure sensitivity tends to increase. The combination of the upper limit and the lower limit is, for example, preferably 100 to 2000 parts by mass, more preferably 130 to 1500 parts by mass, even more preferably 160 to 1000 parts by mass, and particularly preferably 200 to 500 parts by mass.

<(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. When it is at least the above lower limit, the sensitivity tends to be high, and when it is at most the above upper limit, curing shrinkage during polymerization tends to be small. The combination of the upper limit and the lower limit is, for example, preferably 2 to 10, more preferably 3 to 10, even more preferably 4 to 8, even more preferably 5 to 8, and particularly 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.
Polybasic carboxylic acid and unsaturated carboxylic acid, the ester obtained by the esterification reaction of the polyhydric hydroxy compound is not necessarily a single substance, but representative specific 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 the photocuring by ultraviolet irradiation is improved and the alkali developability is also improved. The penetrability of the developing solution is moderate, and it tends to be possible to obtain good images. 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. Especially preferred, 5 to 10% by weight is most preferred.

<(c) Photoradical polymerization initiator>
The photosensitive resin composition of the present invention contains (c) a radical photopolymerization initiator. A photoradical polymerization initiator is a component that has the function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating polymerization active radicals. If necessary, an additive such as a sensitizing dye may be added for use.

Examples of photoradical polymerization initiators include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; JP-A-2000-56118. Hexaarylbiimidazole derivatives described in publications; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-aryl-α- such as N-phenylglycine described in JP-A-10-39503 Radical activators such as amino acids, N-aryl-α-amino acid salts, and N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; JP-A-2000-80068, JP-A-2006 and oxime ester derivatives described in JP-A-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), dicyclopentadienyltitanium bis[2,6-difluoro-3-(1-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 the radical photopolymerization initiator, oxime derivatives (oxime ester compounds and ketoxime ester compounds) are particularly effective in terms of sensitivity. Among oxime derivatives, oxime ester compounds are particularly preferred from the viewpoint of adhesion to substrates.
Oxime ester compounds have a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals, so they are highly sensitive even in small amounts and are stable against thermal reactions. It is possible to design a photosensitive resin composition with a small amount and high sensitivity. In particular, in the case of an oxime ester compound containing an optionally substituted carbazolyl group (a group having an optionally substituted carbazole ring), from the viewpoint of light absorption for the i-line (365 nm) of the exposure light source, This structural characteristic is well expressed, which is more preferable. At present, the market demands BM with a high degree of light shielding and a thin film, and the content of coloring materials is also increasing more and more. It is particularly effective in such circumstances.

Examples of the oxime ester-based compound include compounds containing a partial structure represented by the following general formula (22), preferably oxime ester-based compounds represented by the following general formula (23).

In the above formula (22), R ²² is an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and an alkenoyl group having 3 to 25 carbon atoms, each of which may be substituted. 3-8 cycloalkanoyl group, C3-20 alkoxycarbonylalkanoyl group, C8-20 phenoxycarbonylalkanoyl group, C3-20 heteroaryloxycarbonylalkanoyl group, C2-10 represents an aminoalkylcarbonyl group, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms.

In formula (23), R ^21a is a hydrogen atom, or an optionally substituted alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 25 carbon atoms, or heteroarylalkyl group having 1 to 20 carbon atoms. , an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms. an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms; R ^21b represents an arbitrary substituent containing an aromatic ring; R ^22a represents the same group as R ²² in formula (22) above.

R ^21a may form a ring together with R ^21b , and the linking group may be an alkylene group having 1 to 10 carbon atoms each optionally having a substituent, or a polyethylene group (-(CH=CH) _r- ), a polyethylene group (-(C≡C) _r- ), or a group formed by combining these (where r is an integer of 0 to 3).
R ²² in the above general formula (22) and R ^22a in the above general formula (23) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or a heteroarylalkanoyl group having 1 to 20 carbon atoms. and a cycloalkanoyl group of.

R ^21a in the general formula (23) is preferably an unsubstituted methyl group, an ethyl group, a linear alkyl group such as a propyl group; a cycloalkylalkyl group; propyl group;
R ^21b in the general formula (23) preferably includes an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, and an optionally substituted phenylsulfide group.

As the oxime ester compound, those containing an optionally substituted carbazolyl group as R ^21b are more preferable for the reasons described above. Furthermore, optionally substituted aryl groups having 6 to 25 carbon atoms, optionally substituted arylcarbonyl groups having 7 to 25 carbon atoms, optionally substituted heteroaryl groups having 5 to 25 carbon atoms, substituted A carbazolyl group having at least one group selected from the group consisting of a heteroarylcarbonyl group having 6 to 25 carbon atoms which may be substituted and a nitro group is preferred. A carbazolyl group having at least one group selected from the group consisting of a benzoyl group, a toluoyl group, a naphthoyl group, a thienylcarbonyl group and a nitro group is particularly preferred. Moreover, it is desirable that these groups are bonded to the 3-position of the carbazolyl group.

Commercially available products of such oxime ester compounds include OXE-02 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Power Electronics New Materials.

Specific examples of the oxime ester compound suitable for the present invention include compounds as exemplified below, but the compounds are not limited to these compounds.

Examples of ketoxime ester compounds include compounds containing a partial structure represented by the following general formula (24), preferably oxime ester compounds represented by the following general formula (25).

In general formula (24) above, R ²⁴ has the same definition as R ²² in general formula (22) above.

In the above general formula (25), R ^23a is an optionally substituted phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a heteroarylalkyl group having 1 to 20 carbon atoms. alkoxycarbonylalkyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, alkylthioalkyl group having 2 to 20 carbon atoms, heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or heteroarylthio an alkyl group, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, It represents a heteroarylyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms.

R ^23b represents any substituent containing an aromatic ring.
R ^23a may form a ring together with R ^23b , and the linking group may be an alkylene group having 1 to 10 carbon atoms each optionally having a substituent, a polyethylene group (-(CH=CH) _r -), a polyethylene group (-(C≡C) _r -), or a group formed by combining these (where r is an integer of 0 to 3).

R ^24a is an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, and a carbon atom, each of which may be substituted. a heteroarylyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an alkylamino group having 2 to 20 carbon atoms; represents a carbonyl group.
R ²⁴ in the above general formula (24) and R ^24a in the above general formula (25) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or a heteroarylalkanoyl group having 1 to 20 carbon atoms. and arylyl groups having 7 to 20 carbon atoms.

R ^23a in the general formula (25) preferably includes an unsubstituted ethyl group, a propyl group and a butyl group; and an ethyl group or a propyl group substituted with a methoxycarbonyl group.
R ^23b in the general formula (25) preferably includes an optionally substituted carbazolyl group and an optionally substituted phenylsulfide group.
Specific examples of the ketoxime ester compounds suitable for the present invention include compounds as exemplified below, but are not limited to these compounds.

Commercially available products of such ketoxime ester compounds include OXE-01 manufactured by BASF Corporation and TR-PBG-305 manufactured by Changzhou Power Electronics New Materials.

These oxime ester compounds and keto oxime ester compounds are themselves known compounds. is a kind of compound of
One of the above oxime derivatives may be used alone, or two or more thereof may be used in combination.

Other photoradical polymerization initiators include benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; - anthraquinone derivatives such as chloroanthraquinone; benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone; 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropyl phenyl) ketone, 1-hydroxy-1-(p-dodecylphenyl) ketone, 2-methyl-(4′-methylthiophenyl)-2-morpholino-1-propanone, 1,1,1-trichloromethyl-(p- acetophenone derivatives such as butylphenyl)ketone; thioxanthone such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone Derivatives; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine; 9,10-dimethyl Also included are phenazine derivatives such as benzphenazine; and anthrone derivatives such as benzanthrone.
Among these radical photopolymerization initiators, oxime derivatives are particularly preferred for the reasons described above.

<Sensitizing dye>
A sensitizing dye corresponding to the wavelength of the light source for image exposure can be used in combination with the radical photopolymerization initiator, if necessary, 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 radical photopolymerization initiator is not particularly limited, but is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more in the total solid of the photosensitive resin composition of the present invention. , More preferably 4% by mass or more, usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, particularly preferably 8% 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 the unexposed portion in the developing solution. The combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, still more preferably 3 to 15% by mass, even more preferably 4 to 10% by mass, and 4 to 8% by mass. Especially preferred.

Further, when a sensitizing dye is used, the content of the sensitizing dye is not particularly limited, but usually 0 to 20% by mass, preferably 0 to 15% by mass, more preferably 0 to 15% by mass, based on the total solid content of the photosensitive resin composition. is 0 to 10% by mass.

<(e) Colorant>
The photosensitive resin composition of the present invention contains (e) a coloring material. A coloring material colors the photosensitive resin composition of the present invention.
As the coloring material (e), pigments and dyes can be used, but pigments are preferable from the viewpoint of heat resistance and light resistance.

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, 58, 59 . Among these, C.I. I. Pigment Green 7, 36, 58, 59 can 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.

Dyes may also be used in addition to these pigments. Examples of dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine 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.

Further, when the photosensitive resin composition of the present invention is used for a light-shielding application such as a resin black matrix of a color filter, a black colorant can be used as the (e) colorant. The black colorant may be a black colorant alone or a mixture of red, green, blue, and the like. 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 ( ) 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, titanium black, perylene black, and lactam black.
Among these (e) colorants, when a black colorant is used, carbon black is preferable from the viewpoint of light shielding rate and image characteristics.

In addition, when carbon black is included, the hydrophobicity of the coating film increases, and the adhesion to the substrate tends to deteriorate. becomes insufficient, and the line width tends to change due to melting in the heat curing step. Therefore, by using the organosilicon vinyl polymer (d-1), the cross-linking reaction progresses at the substrate interface and inside the coating film at the start of heating, and these problems are solved. It tends to be compatible with suppression of line width change over time.

Examples of carbon black include the following.
Mitsubishi Chemical Corporation: MA7, MA77, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350 , #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B
Degussa: Printex (registered trademark; hereinafter the same) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, PrintexPrintxL, PrintexPrintxL, PrintexPrintx Ｕ、Ｐｒｉｎｔｅｘ Ｖ、ＰｒｉｎｔｅｘＧ、ＳｐｅｃｉａｌＢｌａｃｋ５５０、ＳｐｅｃｉａｌＢｌａｃｋ３５０、ＳｐｅｃｉａｌＢｌａｃｋ２５０、ＳｐｅｃｉａｌＢｌａｃｋ１００、ＳｐｅｃｉａｌＢｌａｃｋ６、ＳｐｅｃｉａｌＢｌａｃｋ５、ＳｐｅｃｉａｌＢｌａｃｋ４、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ１、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ２、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ２Ｖ、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ１８、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ１８、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ２００、Ｃｏｌｏｒ Ｂｌａｃｋ Ｓ１６０、Ｃｏｌｏｒ Black S170
Cabot Corporation: Monarch (registered trademark; the same shall apply hereinafter) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark; the same shall apply hereinafter) 99, REGAL45REGAL99 REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN® XC72R, ELFTEX®-8

ビルラー社製：ＲＡＶＥＮ１１、ＲＡＶＥＮ１４、ＲＡＶＥＮ１５、ＲＡＶＥＮ１６、ＲＡＶＥＮ２２ＲＡＶＥＮ３０、ＲＡＶＥＮ３５、ＲＡＶＥＮ４０、ＲＡＶＥＮ４１０、ＲＡＶＥＮ４２０、ＲＡＶＥＮ４５０、ＲＡＶＥＮ５００、ＲＡＶＥＮ７８０、ＲＡＶＥＮ８５０、ＲＡＶＥＮ８９０Ｈ、ＲＡＶＥＮ１０００、ＲＡＶＥＮ１０２０、ＲＡＶＥＮ１０４０、ＲＡＶＥＮ１０６０Ｕ、ＲＡＶＥＮ１０８０Ｕ、ＲＡＶＥＮ１１７０、ＲＡＶＥＮ１１９０Ｕ、ＲＡＶＥＮ１２５０、ＲＡＶＥＮ１５００、 RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

Carbon black that is coated with a resin may be used. The use of resin-coated carbon black has the effect of improving the adhesion to the glass substrate and the volume resistivity. As the resin-coated carbon black, for example, carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be preferably used.
The carbon black to be coated preferably has a total content of Na and Ca of 100 ppm or less. Carbon black usually contains Na, Ca, K, Mg, Al, Fe, etc. mixed from raw material oil, combustion oil (or gas), reaction stop water, granulation water, and furnace materials of reactors during normal production. The composition contains ash on the order of percent. Of these, Na and Ca are generally contained in amounts of several hundred ppm or more each. This is because there are cases where

As a method for reducing the content of ash containing these Na and Ca, carefully select those with as little content as possible as raw material oil, fuel oil (or gas) and reaction stop water when producing carbon black. and by minimizing the amount of the alkaline substance added to adjust the structure. Another method is to wash the carbon black produced from the furnace with water or hydrochloric acid to dissolve and remove Na and Ca.

(E) The content of the coloring material is not particularly limited, but is preferably 1% by mass or more, more preferably 20% by mass or more, more preferably 40% by mass or more, and 45% by mass in the total solid content of the photosensitive resin composition % or more is more preferable, 50% by mass or more is particularly preferable, 70% by mass or less is preferable, 60% by mass or less is more preferable, and 55% by mass or less is even more preferable. When the content is at least the above lower limit, the coloring property tends to be improved, and when the content is at most the above upper limit, the pattern formability and substrate adhesion tend to be improved. A combination of the upper limit and the lower limit is, for example, preferably 1 to 70% by mass, more preferably 20 to 60% by mass, still more preferably 45 to 60% by mass, and particularly preferably 50 to 55% by mass.

Further, when the (e) colorant contains carbon black, the content of carbon black is not particularly limited, but is preferably 35% by mass or more, more preferably 45% by mass or more, in the total solid content in the photosensitive resin composition. It is preferably 50% by mass or more, more preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less. When the content is equal to or higher than the lower limit, the light-shielding property tends to be enhanced, and when the content is equal to or lower than the upper limit, pattern formability and substrate adhesion tend to be improved. A combination of the upper limit and the lower limit is, for example, preferably 35 to 70% by mass, more preferably 40 to 60% by mass, and even more preferably 50 to 55% by mass.

In the photosensitive resin composition, the content of (e) the coloring material is usually 20 to 500 parts by mass, preferably 30 to 300 parts by mass, more preferably 40 to 280 parts by mass per 100 parts by mass of the (a) alkali-soluble resin. 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.

<(f) Dispersant>
In the present invention, it is important to finely disperse (e) the coloring material and stabilize the dispersion state in order to ensure the stability of the quality, so (f) 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 BV (EFKA)), DISPERBYK (registered trademark, manufactured by BYK-Chemie), and Disparon (registered trademark, 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 the (f) 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. (all of which are acrylic-based) (all of which are manufactured by BYK-Chemie). Particularly preferred urethane polymer dispersants having a polyester and/or polyether bond and having a weight average molecular weight of 30,000 or less include DISPERBYK 167, 182, and the like.

<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 preferable polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or 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. is 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 hydrogen atoms in functional groups 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 preferable 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 content is equal to or higher than the lower limit, the dispersibility tends to be improved, and when the content is equal to or lower than the upper limit, the developability tends to be improved.

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 content to the lower limit or more, and the solubility tends to be improved by setting the content 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, 182 (Byk-Chemie).

When the photosensitive resin composition of the present invention contains (f) a dispersant, the content of (f) dispersant is usually 1% by mass or more, preferably 3% by mass, in the total solid content of the photosensitive resin composition. % or more, more preferably 5% by mass or more, more preferably 7% by mass or more, and usually 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass. Below, particularly preferably, it is 10% by mass or less. 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. The combination of the upper limit and the lower limit is, for example, 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 15% by mass, and 7 to 10% by mass. % is particularly preferred.

Further, when the photosensitive resin composition of the present invention contains (f) a dispersant, the content of (f) dispersant is usually 5 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of (e) coloring material The amount is preferably 200 parts by mass or less, preferably 80 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less. 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. A combination of the upper limit and the lower limit is, for example, preferably 5 to 200 parts by mass, more preferably 5 to 80 parts by mass, even more preferably 10 to 50 parts by mass, and particularly preferably 10 to 30 parts by mass.

<Thiols>
The photosensitive resin composition of the present invention preferably contains thiols in order to increase sensitivity and improve adhesion to substrates. Types 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 usually 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.3% by mass or more, based on the total solid content of the photosensitive resin composition of the present invention. It is 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 generally comprises (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photoradical polymerization initiator, (d) an organosilicon compound, (e) a coloring material and necessary Various components are 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 constituent 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 the 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 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 setting the content of the high-boiling-point solvent to the above lower limit or more, there is a tendency to suppress, for example, the deposition and solidification of the coloring material at the tip of the slit nozzle to cause foreign matter defects. By doing so, it is possible to suppress the drying rate of the composition from becoming too slow, and there is a tendency to easily avoid problems such as tact failure in the vacuum drying process and pin marks in prebaking 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. A combination of the upper limit and the lower limit is, for example, preferably 5 to 40% by mass, more preferably 8 to 30% by mass, still more preferably 10 to 25% by mass, and particularly preferably 10 to 20% by mass.

<Other compounding components of the photosensitive resin composition>
In the photosensitive resin composition of the present invention, in addition to the above-mentioned components, an adhesion improver, a surfactant (applicability improver), a pigment derivative, a development improver, an ultraviolet absorber, an antioxidant, etc. are appropriately blended. can do.

<Adhesion improver>
In order to improve the adhesion to the substrate, (d) an adhesion improver other than the organosilicon compound may be included, such as 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, R ⁵¹ represents a hydrogen atom or a methyl group, l and l' are integers of 1 to 10, and m is 1, 2 or 3.
Other adhesion improvers include TEGO ^* 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.

<Surfactant>
The photosensitive resin composition of the present invention may contain a surfactant in order to improve coating properties. 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 silicon-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.), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Dow Corning Toray), DS-401 (manufactured by 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 ratios.
When the photosensitive resin composition of the present invention contains a surfactant, the content ratio is not particularly limited, but it is preferably 0.01% by mass or more in the total solid content of the photosensitive resin composition. It is more preferably 0.05% by mass or more, preferably 1.0% by mass or less, more preferably 0.7% by mass or less, and further preferably 0.5% by mass or less. It is preferably 0.3% 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. As a combination of the upper limit and the lower limit, for example, 0.01 to 1.0% by mass is preferable, 0.01 to 0.7% by mass is more preferable, 0.05 to 0.5% by mass is more preferable, and 0.05% to 0.5% by mass is more preferable. 05 to 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 ratio is not particularly limited, but it is usually 0.1% by mass or more in the total solid content of the photosensitive resin composition of the present invention, preferably is 0.5% by mass or more, usually 10% by mass or less, preferably 5% by mass or less. 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.

<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 3.0 or more, and 4 It is particularly preferably 0.0 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, (e) 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 (e) colorant 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 (e), it contributes to the improvement of the light shielding ability.

Dispersion treatment is usually preferably carried out in a system in which (e) a coloring material, an organic solvent, and optionally (f) 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 (e) 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, which is composed of the cured product of the present invention, will be described according to its production method.

(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 if necessary, thermal curing or photocuring.

(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

If the thickness of the coating film is too thick, it may become difficult to develop the pattern and it may be difficult to adjust the gap in the liquid crystal cell formation process. may not be possible. 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 0.5 to 4 μm. Range.

(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 irradiating and using 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 0.7 to 4 μm, more preferably 0.8 to 2 μm.
Furthermore, the optical density (OD) per 1 μm of thickness is 3.0 or more, preferably 3.5 or more, more preferably 3.8 or more, and particularly preferably 4.0 or more.

[Formation of other color filter images]
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.

Color filters are used as parts of color displays, liquid crystal display devices, etc. by forming transparent electrodes such as ITO on the image as they are. A topcoat layer of polyamide, polyimide, or the like may be provided on the image depending on the application. In addition, in some applications such as planar alignment driving system (IPS mode), the transparent electrode may not be formed.

[Colored spacer]
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.

[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 examples and comparative examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

<Preparation of carbon black ink>
A carbon black ink was prepared by blending a pigment, a dispersant, a dispersing aid, and a solvent according to the following composition and method. Specifically, first, the solid content of the pigment, the dispersant, and the dispersing aid and the solvent were mixed so as to have the following mass ratio.
・ Pigment: RAVEN1060U (R1060) (carbon black manufactured by Birler); 100.0 parts by mass ・ Dispersant: DISPERBYK-167 (basic urethane-based dispersant manufactured by BYK-Chemie); 14.0 parts by mass (solid content conversion)
Dispersing aid (pigment derivative): Solsperse 12000 (manufactured by Lubrizol, phthalocyanine pigment derivative having an acidic group); 2.0 parts by mass Solvent: propylene glycol monomethyl ether acetate (PGMEA); 215.5 parts by mass

These were sufficiently stirred and mixed to obtain a dispersion liquid.
Next, this dispersion was subjected to dispersion treatment for 6 hours at a temperature of 25 to 45° C. using a paint shaker. As the beads, zirconia beads with a diameter of 0.5 mm were used, and 180 parts by mass of the beads were added to 60 parts by mass of the dispersion. After completion of the dispersion treatment, the beads and the dispersion liquid were separated by a filter to prepare a carbon black ink having a total solid content of 35% by mass.

<Alkali-soluble resin (1)>
Alkali-soluble resin (1) was synthesized by the following procedure.

50 g of the epoxy compound having the above chemical 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, stirrer, and cooling. The mixture was placed in a flask equipped with a tube and 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 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) 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.

<Alkali-soluble resin (2)>
Alkali-soluble resin (2) was synthesized by the following procedure.

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.

<Alkali-soluble resin (3)>
Alkali-soluble resin (3) was synthesized by the following procedure.
114.0 g of propylene glycol monomethyl ether acetate was placed in a 500 mL four-necked flask and heated to 85° C. while bubbling with nitrogen. To this, 96.8 g (0.55 mol) of benzyl methacrylate, 33.3 g (0.45 mol) of methacrylic acid, and 4.93 g (0.03 mol) of 2,2'-azobis(isobutyronitrile) were added to propylene glycol monomethyl ether acetate. A solution of 96.45 g was added dropwise over 4 hours. After dropping, the reaction solution was stirred for 2 hours while maintaining the temperature at 85°C, then nitrogen bubbling was stopped, the temperature was raised to 100°C, and the mixture was stirred for 1 hour to react. An alkali-soluble resin (3) having a polystyrene equivalent weight average molecular weight (Mw) of 15,000 was obtained.

<Alkali-soluble resin (4)>
Alkali-soluble resin (4) was synthesized by the following procedure.

Epoxy compound having the above chemical structure (NC-3000-H, manufactured by Nippon Kayaku Co., Ltd.) 400 parts by mass, acrylic acid 100 parts by mass, p-methoxyphenol 0.3 parts by mass, triphenylphosphine 5 parts by mass, propylene glycol monomethyl ether 264 parts by mass of acetate was charged into a reaction vessel and stirred at 95° C. until the acid value became 3 mgKOH/g or less. It took 9 hours to reach the target acid value of 2.2 mgKOH/g. Then, 190 parts by mass of tetrahydrophthalic anhydride was added and reacted at 95° C. for 4 hours to obtain an alkali-soluble resin (4) having an acid value of 98 mgKOH/g and a polystyrene-equivalent weight average molecular weight (Mw) of 4500 measured by GPC. rice field.

<Alkali-soluble resin (5)>
Alkali-soluble resin (5) was synthesized by the following procedure.

235 g of the epoxy compound (bisphenol fluorene type epoxy resin, epoxy equivalent: 235) having the above chemical structure, 3.73 g of triphenylphosphine, 100 mg of 2,6-di-tertbutyl-4-methylphenol and 72.0 g of acrylic acid in four 500 ml portions The solution was placed in a necked flask, heated at 90 to 100° C. while blowing nitrogen containing 5% oxygen, and then heated to 120° C. for complete dissolution. The acid value was measured, and heating and stirring were continued until it became less than 1.0 mgKOH/g. It took 12 hours for the acid value to reach the target. After cooling to room temperature, a colorless and transparent solid bisphenol fluorene type epoxy acrylate was obtained. Next, 600 g of propylene glycol monomethyl ether acetate was added to 307.0 g of the bisphenol fluorene type epoxy acrylate thus obtained and dissolved, and then 80.5 g of benzophenonetetracarboxylic dianhydride was mixed and gradually The temperature was raised and the reaction was carried out at 110-115°C. Then, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and allowed to react at 90° C. Solid content of 41.5% by mass, acid value of 100 mgKOH/g, weight average in terms of polystyrene measured by GPC. An alkali-soluble resin (5) having a molecular weight (Mw) of 5000 was obtained.

<Photopolymerizable monomers (1) and (2)>
The following photopolymerizable monomers were prepared.
Photopolymerizable monomer (1): KAYARAD DPCA20 (manufactured by Nippon Kayaku Co., Ltd.)

Photopolymerizable monomer (2): Light acrylate PE4A (pentaerythritol tetraacrylate) (manufactured by Kyoeisha Chemical Co., Ltd.)

<Photoradical polymerization initiator (1)>
The following radical photopolymerization initiator (1) was prepared.
Photoradical polymerization initiator (1): TR-PBG-314 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.)

<Organosilicon Vinyl Polymers (1) to (4)>
As the organosilicon vinyl polymer (d-1), organosilicon vinyl polymers (1) to (4) were prepared by the following procedure.

Organosilicon vinyl polymer (1):
200 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent was weighed into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and the mixture was stirred while being replaced with nitrogen and heated to 120°C. Next, KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd., a compound of the following formula (d1). In the formula, C ₃ H ₆ represents an n-propane-1,3-diyl group.) 111.6 g and methacrylic acid A polymerizable monomer mixture containing 45.0 g of methyl (MMA, compound of the following formula (d2)) (mixing molar ratio: KBM-503:MMA = 50:50) was added with a thermal radical polymerization initiator t-butylhydroper 7.0 g of oxide (PERBUTYL O manufactured by NOF Corporation) was added and mixed. This mixture was added dropwise from the dropping funnel to the flask over 2 hours, stirred at 120° C. for 2 hours, and then returned to room temperature to obtain a copolymer having a repeating unit represented by the following formula (d3) (m:n = 50:50) solution was obtained. The solid content concentration of the obtained copolymer solution was 45% by mass. Further, the weight average molecular weight (Mw) of polystyrene equivalent measured by GPC of the copolymer was 12,000.

Organosilicon vinyl polymer (2):
In the synthesis of the organosilicon vinyl polymer (1), except that 89.6 g of KBM-503 and 67.0 g of MMA (mixing molar ratio of KBM-503:MMA = 35:65) were changed and added. A solution of a copolymer (m:n=35:65) having repeating units represented by the above formula (d3) was obtained in a similar manner. The solid content concentration of the obtained copolymer solution was 45% by mass. Moreover, the weight average molecular weight (Mw) of polystyrene conversion of the copolymer measured by GPC was 12,000.

Organosilicon vinyl polymer (3):
In the synthesis of the organosilicon vinyl polymer (1), except that 133.5 g of KBM-503 and 23.1 g of MMA (mixing molar ratio of KBM-503:MMA = 70:30) were added. A solution of a copolymer (m:n=70:30) having repeating units represented by the above formula (d3) was obtained in the same manner. The solid content concentration of the obtained copolymer solution was 45% by mass. Moreover, the weight average molecular weight (Mw) of polystyrene conversion of the copolymer measured by GPC was 12,000.

Organosilicon vinyl polymer (4):
In the synthesis of the organosilicon vinyl polymer (1), 78.3 g of KBM-503, 15.8 g of MMA, and 62.5 g of Light Ester 130MA (manufactured by Kyoeisha Chemical Co., Ltd., compound of the following formula (d4)) (mixed A copolymer having a repeating unit represented by the following formula (d5) ( p:q:r=50:25:25) was obtained. The solid content concentration of the obtained copolymer solution was 45% by mass. Moreover, the weight average molecular weight (Mw) of polystyrene conversion of the copolymer measured by GPC was 12,000.

<Other organosilicon compounds>
The following organosilicon compounds were prepared.
Organosilicon compound (1): a compound having the following chemical structure (wherein C ₂ H ₄ represents a 1,2-ethylene group and C ₃ H ₆ represents an n-propane-1,3-diyl group .)

Organosilicon compound (2): Z-6040 (manufactured by Dow Corning Toray Co., Ltd.) (In the formula, C ₃ H ₆ represents an n-propane-1,3-diyl group.)

<Surfactant>
As a surfactant, the following surfactant (1) was prepared.
Surfactant (1): Megafac F-554 (manufactured by DIC, fluorine-based surfactant)

<Example 1>
(Preparation of black resist 1)
Using the carbon black ink prepared in the above <Preparation of carbon black ink>, each component was added so that the proportions shown in Table 1 were obtained, and the components were stirred with a stirrer to dissolve or disperse the black resist 1. prepared. The content ratio of the total solid content in the black resist 1 is 15% by mass.

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

<Example 2>
(Preparation of black resist 2)
Black resist 2 was prepared in the same manner as black resist 1 of Example 1, except that organosilicon vinyl polymer (1) was changed to organosilicon vinyl polymer (2).

<Example 3>
(Preparation of black resist 3)
Black Resist 3 was prepared in the same manner as Black Resist 1 of Example 1, except that Organosilicon Vinyl Polymer (1) was changed to Organosilicon Vinyl Polymer (3).

<Example 4>
(Preparation of black resist 4)
In Example 1, the amount of the organosilicon vinyl polymer (1) was reduced to 0.75% by mass in the total solid content, and the amount of the alkali-soluble resin (1) was 18.15 in the total solid content. A black resist 4 was prepared in the same manner as the black resist 1 of Example 1, except that the amount was increased so as to be 1% by mass.

<Example 5>
(Preparation of black resist 5)
In Example 1, the amount of the organosilicon vinyl polymer (1) was increased to 3.00% by mass based on the total solid content, and the amount of the alkali-soluble resin (1) was increased to 15.90% based on the total solid content. A black resist 5 was prepared in the same manner as the black resist 1 of Example 1, except that the weight was reduced to 1% by mass.

<Example 6>
(Preparation of black resist 6)
A black resist 6 was prepared in the same manner as the black resist 1 of Example 1, except that the organosilicon vinyl polymer (1) was changed to the organosilicon vinyl polymer (4).

<Example 7>
(Preparation of black resist 7)
Black resist in the same manner as black resist 1 of Example 1, except that the total amount (solid content) of the alkali-soluble resin (1) and the alkali-soluble resin (2) was changed to the alkali-soluble resin (4) in Example 1. 7 was prepared.

<Example 8>
(Preparation of black resist 8)
Black resist in the same manner as black resist 1 of Example 1, except that the total amount (solid content) of the alkali-soluble resin (1) and the alkali-soluble resin (2) was changed to the alkali-soluble resin (5) in Example 1. 8 was prepared.

<Comparative Example 1>
(Preparation of black resist 9)
Example 1 except that the organosilicon vinyl polymer (1) was not added (PGMEA was added to the 1.5% by mass of the organosilicon vinyl polymer (1)). Black resist 9 was prepared in the same manner as black resist 1 of No. 1.

<Comparative Example 2>
(Preparation of black resist 10)
A black resist 10 was prepared in the same manner as the black resist 1 of Example 1, except that the organosilicon vinyl polymer (1) was changed to the organosilicon compound (1).

<Comparative Example 3>
(Preparation of black resist 11)
A black resist 11 was prepared in the same manner as the black resist 1 of Example 1, except that the organosilicon vinyl polymer (1) was changed to the organosilicon compound (2).

<Comparative Example 4>
(Preparation of black resist 12)
Black resist in the same manner as black resist 1 of Example 1, except that the total amount (solid content) of the alkali-soluble resin (1) and the alkali-soluble resin (2) was changed to the alkali-soluble resin (3) in Example 1. 12 was prepared.

(Evaluation of resist)
(1) Preparation of Black Resist Cured Film The prepared black resists 1 to 12 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 each coating film thickness 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.) with 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, using a KOH aqueous solution adjusted to 0.04% by mass with ultrapure water as an alkaline developer, at room temperature (23 ° C.), spray development for 1.8 times the dissolution time (spray pressure: 0.1 MPa ), and further subjected to spray cleaning with ultrapure water (spray pressure: 0.1 MPa) to obtain a black resist film. After that, heat curing was performed in an oven at 230° C. for 30 minutes to prepare a substrate with a black resist cured 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 entire substrate begins to be visible during development, and the dissolution time of each black resist was between 38 and 67 seconds.
The film thickness of the cured black resist film was measured with a step measuring device Alpha-Step-500 (manufactured by KLA-Tencor) after a part of the film was shaved with a cutter to provide a stepped portion. Incidentally, the film thickness can be adjusted by changing the rotation speed of the spin coater.

(2) Evaluation of substrate adhesion For each substrate with a black resist cured film prepared in (1) above, after returning to room temperature, a 2.5 cm square measurement substrate was cut out, and the thermosetting sealant Structbond XN- 21-S (manufactured by Mitsui Chemicals, Inc.) was used to join aluminum stud pins (P/N: 901106U, diameter 2.7 mm, manufactured by Quad Group) to prepare a sample for measurement. The prepared sample was subjected to a tensile test at a speed of 2.0 kg/s using a thin film adhesion strength measuring machine Romulus (manufactured by Quad Group), and the breaking strength and breaking strength when the cured black resist film and the glass substrate broke. The substrate adhesion stress was obtained from the adhesion area by the following formula.
Substrate adhesion stress (kg/cm ² )=breaking strength (kg)/adhesion area (cm ² )

From this, the substrate adhesion strength (%) was obtained as a relative value (%) when the value of the substrate adhesion stress (kg/cm ² ) in Comparative Example 1 was taken as 100%. The results and evaluation results are shown in Table 2. Evaluation criteria are as follows.

(Evaluation Criteria for Substrate Adhesion)
· A: Substrate adhesion strength is 150% or more.
*B: Substrate adhesion strength is 120% or more and less than 150%.
· C: Substrate adhesion strength is 110% or more and less than 120%.
*D: Substrate adhesion strength is less than 110%.

(3) Preparation of black matrix (BM) cured film For the dried 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 through an exposure mask having linear openings with a pattern width of 8 μm (proximity gap: 180 μm). After that, using a KOH aqueous solution adjusted to 0.04% by mass with ultrapure water as an alkaline developer, at room temperature (23 ° C.), spray development for 1.8 times the dissolution time (spray pressure: 0.1 MPa ), and further spray-cleaned 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.

(4) Evaluation of BM Line Width Change Amount The line width of the BM line pattern in the BM film and the BM cured film was measured with an optical microscope, and the line width change before and after heat curing was measured. The results are shown in Table 2.

(5) Evaluation of BM Line Width When the line width of the BM film of Example 6 was measured, the line width was increased by 0.5 μm from that of the BM film of Comparative Example 1.

As shown in Table 2, the photosensitive resin compositions of the present invention (Examples 1 to 8) contained the organosilicon vinyl polymer (d-1), thereby improving adhesion to the substrate after heat curing. is doing. Furthermore, it was possible to control the amount of change in line width before and after heat curing to narrow it, and in particular, it was confirmed that the amount of change in line width decreased by increasing the amount of addition.

On the other hand, in Comparative Example 1, since the (d) organosilicon compound was not included at all, the adhesion to the substrate was low.
Further, in Comparative Examples 2 and 3, since the organosilicon compounds (1) and (2), which are silane coupling agents, are included, the substrate adhesion is evaluated as A to B, and the substrate adhesion performance is improved compared to Comparative Example 1. I know you are. On the other hand, the amount of change in line width of the BM line is about the same as in Comparative Example 1, indicating that there is no particular effect of addition.

On the other hand, in Comparative Example 4, although the substrate adhesion was evaluated as A due to the inclusion of the organosilicon vinyl polymer (d-1), (a) the epoxy (meth)acrylate resin having a carboxyl group was used as the alkali-soluble resin. Since it is not contained, the BM line line width variation is large, indicating that the effect of suppressing line width variation by the organosilicon vinyl polymer (d-1) is small.

On the other hand, in Examples 1 to 8, the addition of the organosilicon vinyl polymer (d-1) resulted in an A evaluation of substrate adhesion, indicating an improvement in substrate adhesion performance. Furthermore, in addition to the organosilicon vinyl polymer (d-1), (a) an epoxy (meth)acrylate resin having a carboxyl group is included as an alkali-soluble resin, so that the line width of the BM line is also improved during heat curing. was found to be effective in suppressing the line width change. In particular, from a comparison of the results of Examples 1, 4 and 5, it is possible to adjust the amount of change in line width by adjusting the amount of addition of the organosilicon vinyl polymer (d-1), and the line width hardly changes as the amount is increased. It turns out that it is also possible to

From the above results, by adding the organosilicon vinyl polymer (d-1) to a photosensitive resin composition containing an epoxy (meth)acrylate resin having a carboxyl group, the adhesion to the substrate is improved and the It can be seen that the line width variation can be adjusted to be smaller. With the diversification of liquid crystal panels, the requirements for the shape of the BM skirt are also diversifying. Melt control makes it possible to adjust the roundness and taper angle of the BM skirt.

The action of the organosilicon vinyl polymer (d-1) in the present invention is considered as follows.
First, when (d) no organosilicon compound is contained, the adhesion to the substrate is due to intermolecular interactions and cannot be said to be sufficient. In addition, in the heat-curing step, it is considered that the resin flow occurs when the softening temperature of the resin component is exceeded during temperature rise, resulting in a large line width change. In particular, when carbon black is included, the hydrophobicity of the coating tends to increase, and substrate adhesion tends to deteriorate. Since the curing is insufficient, the line width tends to change in the heat curing process.

On the other hand, when (d) an organosilicon compound is included, it can form a chemical bond with the surface of an inorganic material substrate such as glass by having a silicon atom-containing functional group such as an alkoxysilyl group. In addition, the functional group binds or interacts with the organic material in the BM film, thereby acting as an intermediary between the organic material and the inorganic material substrate, thereby contributing to the improvement of substrate adhesion. This is common to Examples 1-8 and Comparative Examples 2-4.

(d) Among the organosilicon compounds, the organosilicon vinyl polymer (d-1) has a plurality of silicon atom-containing side chains such as alkoxysilyl groups in the molecule, so that multi-point bonding with the inorganic material substrate is possible and contributes to the improvement of substrate adhesion.
Furthermore, the silicon atom-containing side chains remaining without bonding to the substrate at multiple points undergo a self-condensation reaction during the temperature rise of the heat curing, cross-linking progresses, and they bond to each other to form a huge three-dimensional structure in the film. It is considered that a network structure (cluster) is formed. It is considered that the gelation of this three-dimensional network structure suppresses the change in line width due to melting. In addition, since it is a vinyl polymer, it can spread in the coating film of the photosensitive resin composition, and a three-dimensional network structure is uniformly formed in the coating film, suppressing line width change. It is considered that it was effectively expressed. Furthermore, by changing the addition amount of the organosilicon vinyl polymer (d-1), it is considered that the size of the clusters formed can also be adjusted and the amount of change in line width can be controlled.
In particular, it is believed that (a) the use of an ethylenically unsaturated group-containing resin as the alkali-soluble resin increased the number of cross-linking points during exposure, resulting in a higher softening start temperature. Among resins with ethylenically unsaturated groups, including epoxy (meth) acrylate resins with carboxyl groups, hydrogen bonding by ester groups, dipole-dipole interactions, and π-π interactions between aromatic rings In addition, hydrogen bonding by carboxyl groups also works, and the free volume between the main chains of the resin decreases, making it difficult for oxygen to permeate. It is considered that the width change is small.

On the other hand, in the case of the organosilicon compounds (1) and (2), which are organosilicon compounds that are not polymers as in Comparative Examples 1 to 3, the original molecular size is small. For this reason, even if the same number of cross-linking reactions as in the case of the organosilicon vinyl polymer (d-1) occur during the heat-curing temperature rise, cluster formation does not occur. It is considered that the influence on the amount of change is minimal.

On the other hand, even if the organosilicon vinyl polymer (d-1) is contained as in Comparative Example 4, when the epoxy (meth)acrylate resin having a carboxyl group is not contained as the alkali-soluble resin, the It is thought that the number of cross-linking points is reduced, and the melting progresses at a temperature lower than the temperature at which the cross-linking reaction between the silicon atom-containing side chains starts, resulting in an increase in the amount of change in line width.

As described above, by using the photosensitive resin composition of the present invention, substrate adhesion is improved, line width change during heat curing can be controlled, and high-definition patterns can be formed.

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 (7)

(a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photoradical polymerization initiator, (d) an organosilicon compound, and (e) a coloring material.
The (a) alkali-soluble resin comprises an epoxy (meth)acrylate resin having a carboxyl group,
The (d) organosilicon compound comprises an organosilicon vinyl polymer (d-1) having a repeating unit represented by the following general formula (1) ,
A photosensitive resin composition , wherein the content of repeating units represented by the general formula (1) is 40 mol% or more in all the repeating units of the organosilicon vinyl polymer (d-1) .

(In formula (1), R ¹ represents a hydrogen atom or an optionally substituted alkyl group, R ² to R ⁴ each independently represents an alkoxy group having 1 to 3 carbon atoms , L represents a divalent linking group, and x represents 0 or 1.) 2. The photosensitive resin composition according to claim 1, wherein the content of the repeating unit represented by the general formula (1) is 90 mol % or less in all the repeating units of the organosilicon vinyl polymer (d-1). thing. 3. The photosensitive resin composition according to claim 1, wherein the epoxy (meth)acrylate resin having a carboxyl group has a partial structure represented by general formula (a1-II) below.

(In formula (a1-II), m and n are 0, and R ¹³ each independently represents a hydrogen atom or a methyl group, and R ¹⁴ connects a divalent aromatic ring group or one or more divalent aliphatic groups and one or more divalent aromatic ring groups having an aliphatic ring group having 8 to 20 carbon atoms as a side chain * represents a bond. ) The photosensitive resin composition according to any one of claims 1 to 3, wherein the (e) colorant contains carbon black. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 4 . A black matrix comprising the cured product according to claim 5 . An image display device comprising the cured product according to claim 5 or the black matrix according to claim 6 .

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