JP6977662B2 - Photosensitive resin composition, cured product and image display device - Google Patents

Description

The present invention relates to a photosensitive resin composition, a cured product, and an image display device. In particular, the present invention relates to a photosensitive resin composition having high sensitivity and excellent fine line adhesion, a cured product obtained by curing the photosensitive resin composition, and an image display device having the cured product. The photosensitive resin composition of the present invention is particularly suitable for a photosensitive resin composition for a black matrix (Black Matrix, hereinafter abbreviated as "BM") capable of forming high-sensitivity and high-definition fine lines. There is.

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

Currently, a pigment dispersion method is known as a typical method for manufacturing a color filter. When a color filter is manufactured by the pigment dispersion method, a photosensitive resin composition containing a black pigment is first applied onto a transparent substrate, dried, and then image-exposed and developed, and then cured by high-temperature treatment at 200 ° C. or higher. This forms a BM. A color filter is formed by repeating this for each color such as red, green, and blue.

The BM is generally arranged in a grid pattern, a stripe pattern, or a mosaic pattern between pixels of red, green, blue, etc., and has a role of improving contrast or preventing light leakage by suppressing color mixing between the pixels. .. Therefore, the BM is required to have a high light-shielding property. Further, since the edge portion of the pixels such as red, green, and blue formed after the BM is partially overlapped with the BM, a step is formed at the overlapped portion due to the influence of the film thickness of the BM. At this overlapping portion, the flatness of the pixels is impaired, non-uniformity of the liquid crystal cell gap or disorder of the orientation of the liquid crystal occurs, which causes a decrease in display capability. Therefore, in recent years, it has been particularly required to reduce the film thickness of BM, and in order to exhibit sufficient light-shielding properties even when the film thickness is reduced, the pigment content ratio in the photosensitive resin composition tends to increase. be. Therefore, the proportion of the photopolymerization initiator that can be added is decreasing, and there is a demand for a highly sensitive initiator that can maintain the degree of cross-linking even if a small amount is added.

On the other hand, in order to save energy and extend the life of the mobile battery, the output of the backlight tends to be low, and the thin line of BM, which is a light-shielding part, can display images with high brightness even under such conditions. Is being promoted. Further, in recent years, in the liquid crystal display market, miniaturization such as tablets has become the mainstream, and the demand for high resolution is increasing in large-sized televisions. For these reasons as well, there is an increasing demand for higher definition of BM, and in recent years, the line width of BM fine lines has been required to be about 6 to 8 μm from the conventional 10 μm. When the pattern line width of the exposure mask is less than 10 μm, the influence of the diffraction of the passed light becomes large, and the amount of light reaching the BM surface is reduced by that amount. Therefore, a highly sensitive initiator is required. Further, in the development after exposure, it is common to set the development time longer in order to eliminate the residue, but this promotes the dissolution (insertion) of the BM / substrate interface and the line pattern is likely to be peeled off. .. When the pattern line width is 10 μm or more, the fine line adhesion can be maintained even if the insertion of about 1 to 2 μm (total of about 2 to 4 μm on both sides of the line) occurs, but the fine line pattern of less than 10 μm has a BM / substrate adhesion area. It becomes smaller, and the reduction width of the development adhesion becomes remarkably large every time the line width is narrowed by 1 μm. In particular, in the shower development method used in a color filter manufacturing apparatus or the like, the physical adhesion of the BM is also required, so that it is difficult to form a fine line pattern of less than 10 μm. Therefore, it is necessary to improve the fine line adhesion by means such as improving the internal curability at the time of exposure.

Against this background, there is a demand for a photosensitive resin composition for BM having high sensitivity and excellent adhesion to fine wires of less than 10 μm.

Patent Document 1 describes that an oxime ester compound having a nitrated carbazolyl structure is a highly sensitive photopolymerization initiator that efficiently absorbs and activates light having a long wavelength such as 405 nm or 365 nm. Patent Document 2 describes that an oxime ester compound having a benzo-unsaturated 5-membered ring-carbonyl group has high sensitivity.

International Publication No. 2008/07878 International Publication No. 2015/036910

When the present inventors performed a BM evaluation using the photopolymerization initiator described in Patent Document 1, it was found that although the sensitivity was high, the fine line adhesion in the shower development method was insufficient. rice field. Further, when a BM evaluation was performed using the photopolymerization initiator described in Patent Document 2, it was found that the fine line adhesion was good, but the line width was narrowed and the film on the pattern top was reduced, and the sensitivity was not sufficient. It was issued.
Therefore, an object of the present invention is to provide a photosensitive resin composition having high sensitivity and excellent fine wire adhesion.

As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by containing a specific combination of photopolymerization initiators in the photosensitive resin composition. That is, the gist of the present invention lies below.

[1] A photosensitive resin composition containing (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, and (d) a coloring material.
The photopolymerization initiator (c) is a photopolymerization initiator (c1) represented by the following general formula (I) and a photopolymerization initiator having a maximum absorption wavelength of 334 nm or more in the wavelength range of 320 nm to 400 nm. A photosensitive resin composition comprising c2).

(In formula (I), R ¹ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ² represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
k represents 0 or 1.
R ^{3 to} R ⁶ each independently represent an arbitrary monovalent substituent.
l, m and o each independently represent an integer of 0 to 3. n represents 0 or 1. )

[2] The photosensitive resin composition according to [1], wherein the content ratio of the photopolymerization initiator (c) to the total solid content is 2% by mass or more.
[3] The photosensitive resin composition according to [1] or [2], wherein the content ratio of the photopolymerization initiator (c1) in the (c) photopolymerization initiator is 1% by mass or more.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the photopolymerization initiator (c2) is a photopolymerization initiator having a fluorene skeleton or a carbazole skeleton.
[5] The photosensitive resin composition according to [4], wherein the photopolymerization initiator (c2) is a photopolymerization initiator represented by the following general formula (II).

(In formula (II), R ⁷ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ⁸ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
p represents 0 or 1.
R ⁹ represents any monovalent substituent. q represents an integer of 0 to 3.
X represents −N (R ¹⁰ ) − or −C (R ¹¹ ) (R ¹² ) −.
R ^{10 to} R ¹² each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R ¹¹ and R ¹² may be coupled to each other to form a ring. )

[6] The photosensitive resin composition according to any one of [1] to [5], wherein the coloring material (d) is carbon black.
[7] The photosensitive resin composition according to any one of [1] to [6], wherein the content ratio of the coloring material (d) to the total solid content is 30% by mass or more.
[8] The photosensitive resin composition according to any one of [1] to [7], wherein the alkali-soluble resin (a) contains an epoxy (meth) acrylate resin having a carboxyl group.
[9] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [8].
[10] An image display device having the cured product according to [9].

According to the present invention, it is possible to provide a photosensitive resin composition having high sensitivity and excellent fine wire adhesion.

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

Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.
In the present invention, "(meth) acrylic" means "acrylic and / or methacrylic", and the same applies to "(meth) acrylate" and "(meth) acryloyl".
Further, in the present invention, all percentages and parts represented by mass are the same as percentages and parts represented by weight.

In the present invention, the "total solid content" means all the 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, the "amine value" represents an amine value in terms of effective solid content, and is a value represented by the amount of base per 1 g of solid content of the dispersant and the weight of equivalent KOH, unless otherwise specified. Is. The measurement method will be described later.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention is a photosensitive resin composition containing (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator and (d) a coloring material. The (c) photopolymerization initiator is a photopolymerization initiator (c1) represented by the following general formula (I), and a photopolymerization initiator having a maximum absorption wavelength of 334 nm or more in the wavelength range of 320 nm to 400 nm. It is characterized by containing c2). In the present invention, the "maximum absorption wavelength" of (c) the photopolymerization initiator means the maximum absorption wavelength in the wavelength range of 320 nm to 400 nm.

In formula (I), R ¹ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ² represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
k represents 0 or 1.
R ^{3 to} R ⁶ each independently represent an arbitrary monovalent substituent.
l, m and o each independently represent an integer of 0 to 3. n represents 0 or 1.

The photosensitive resin composition of the present invention may further contain a dispersant and thiols, and if necessary, an adhesion improver, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, and the like. Other compounding components such as pigment derivatives may be contained, and each compounding component is usually used in a state of being dissolved or dispersed in an organic solvent.
A feature of the present invention is that the (c) photopolymerization initiator contains a photopolymerization initiator (c1) and a photopolymerization initiator (c2) in the photosensitive resin composition. First, (c) a photopolymerization initiator will be described.

<(C) Photopolymerization initiator>
The (c) photopolymerization initiator in the present invention contains a photopolymerization initiator (c1) represented by the general formula (I) described later and a photopolymerization initiator (c2) having a maximum absorption wavelength of 334 nm or more. do.

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

In formula (I), R ¹ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ² represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
k represents 0 or 1.
R ^{3 to} R ⁶ each independently represent an arbitrary monovalent substituent.
l, m and o each independently represent an integer of 0 to 3. n represents 0 or 1.

As described above, by containing the photopolymerization initiator (c1) represented by the general formula (I), the adsorption of the photopolymerization initiator on the surface of the coloring material particles is promoted, and the photopolymerization initiator at the time of exposure is promoted. It is considered that the light absorption rate of the polymer is improved, the UV (Ultraviolet) light transmittance of the resin component is increased, the internal curability is improved, and the fine line adhesion is improved.

(R ¹ )
In the formula (I), R ¹ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
The alkyl group in R ¹ may be linear, branched, cyclic, or bonded to each other. The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 12 or less, more preferably 6 or less, still more preferably 3 or less, and particularly preferably 2 or less. By setting the number of carbon atoms of the alkyl group to the upper limit or less, the crosslink density tends to increase.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group and the like. Among these, from the viewpoint of sensitivity, a methyl group, an ethyl group, a propyl group, or a butyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is further preferable.
Examples of the substituent that the alkyl group may have include an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a halogen atom such as F, Cl, Br, and I, a hydroxyl group, and a nitro group. From the viewpoint of solvent solubility, a methoxy group or a hydroxyl group is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.

Examples of the aromatic ring group in R ¹ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, still more preferably 8 or less. When the number of carbon atoms of the aromatic ring group is at least the above lower limit value, the storage stability tends to be good, and when it is at least the above upper limit value, the solvent solubility tends to be good.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have one free atomic value. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free atomic value. Ring, Pyrolobymidazole ring, Pyrrolopyrazole ring, Pyrrolopyrrole ring, Thienopyrrole ring, Thienothiophene ring, Flopyrole ring, Flofran ring, Thienofranc ring, Benzoisoxazole ring, Benzoisothiazole ring, Benzimidazole ring, Pyridine ring, Pyrazine ring, Examples thereof include pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, sinoline rings, quinoxalin rings, phenanthridin rings, benzimidazole rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings.
Among these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having one free valence is preferable, and a benzene ring having one free valence is more preferable.

Substituents that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, and I. Examples thereof include halogen atoms such as, hydroxyl groups and nitro groups, and methoxy groups or hydroxyl groups are preferable from the viewpoint of solvent solubility. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.

Among these, from the viewpoint of curability, R ¹ is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and further preferably a methyl group.

(R ² )
In the formula (I), R ² represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
The alkyl group in R ² can be linear, even branched, be cyclic, may be one to which they are attached, but solvent solubility viewpoint from straight or branched is preferred, branched and more preferable.
The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, particularly preferably 5 or more, and preferably 10 or less, more preferably 8 or less. , More preferably 7 or less, and particularly preferably 6 or less. When the number of carbon atoms of the alkyl group is at least the above lower limit value, the solvent solubility tends to be good, and when it is at least the above upper limit value, the sensitivity tends to be high.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group and the like. Among these, from the viewpoint of solvent solubility, an isopropyl group, an isobutyl group, an isopentyl group, or a cyclopentyl group is preferable, an isobutyl group or an isopentyl group is more preferable, and an isopentyl group is further preferable.
Substituents that the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, and I. Examples thereof include halogen atoms and hydroxyl groups such as, and from the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.

The aromatic ring group in R ^2, an aromatic hydrocarbon ring group and aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, still more preferably 8 or less. When the number of carbon atoms of the aromatic ring group is at least the above lower limit value, the molecule tends to be stable, and when it is at least the above upper limit value, the solvent solubility tends to be good.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have one free atomic value. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free atomic value. Ring, Pyrolobymidazole ring, Pyrrolopyrazole ring, Pyrrolopyrrole ring, Thienopyrrole ring, Thienothiophene ring, Flopyrole ring, Flofran ring, Thienofranc ring, Benzoisoxazole ring, Benzoisothiazole ring, Benzimidazole ring, Pyridine ring, Pyrazine ring, Examples thereof include pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, sinoline rings, quinoxalin rings, phenanthridin rings, benzimidazole rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings.
Among these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having one free valence is preferable, and a benzene ring having one free valence is more preferable.

Substituents that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, and I. Examples thereof include a halogen atom such as, a hydroxyl group and a nitro group, and from the viewpoint of solvent solubility, an alkoxy group or a hydroxyl group having 1 to 3 carbon atoms is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.

Among these, from the viewpoint of sensitivity, R ² is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and further preferably an isopentyl group.

(K)
In the formula (I), k represents 0 or 1. From the viewpoint of sensitivity, k is preferably 0, while from the viewpoint of solvent solubility, k is preferably 1.

(R ^{3 to} R ⁶ )
In the formula (I), R ^{3 to} R ⁶ each independently represent an arbitrary monovalent substituent.
As any monovalent substituent, an alkyl group having 1 to 10 carbon atoms such as a methyl group and an ethyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; F, Cl, Br, I and the like. Halogen atom; acyl group having 1 to 10 carbon atoms; alkyl ester group having 1 to 10 carbon atoms; alkoxycarbonyl group having 1 to 10 carbon atoms; alkyl halide group having 1 to 10 carbon atoms; 4 to 10 carbon atoms Examples include an aromatic ring group; an amino group; an aminoalkyl group having 1 to 10 carbon atoms; a hydroxyl group; a nitro group; a CN group and the like. Among these, a methyl group and a methoxy group are preferable, and a methyl group is more preferable, from the viewpoint of solvent solubility.
In R ³ , R ⁴ and R ⁶ , when l, m and o are 2 or more, a plurality of R ³ , R ⁴ and R ⁶ may be bonded to each other to form a ring. The ring may be an aliphatic ring or an aromatic ring.

(L, m, n, o)
In the formula (I), l, m and o each independently represent an integer of 0 to 3, and n represents 0 or 1.
From the viewpoint of sensitivity, l, m and o are preferably 0 or 1 independently, and more preferably 0. Further, from the viewpoint of sensitivity, n is preferably 0.

The photopolymerization initiator represented by the general formula (I) is represented by the following general formula (I-1) from the viewpoint of a balance between solvent solubility and sensitivity and an appropriate interaction with a coloring material. It is preferably a photopolymerization initiator.

In the formula (I-1), R ^{1 to} R ⁶ and k to o are synonymous with the above formula (I).

The maximum absorption wavelength of the photopolymerization initiator (c1) is not particularly limited, but from the viewpoint of sensitivity, it is preferably 322 nm or more, more preferably 325 nm or more, further preferably 328 nm or more, further preferably 329 nm or more, and 330 nm or more. Particularly preferably, it is preferably 337 nm or less, more preferably 336 nm or less, further preferably 334 nm or less, still more preferably 333 nm or less. Within the above range, there is a tendency that the light between the emission line of 333 nm and the emission line (i line) of 365 nm emitted by the UV light source can be effectively used.

The method for producing the photopolymerization initiator (c1) is not particularly limited, and for example, the method described in International Publication No. 2015/036910 can be adopted.
Further, specific examples of the photopolymerization initiator (c1) include the following.

In addition to the photopolymerization initiator (c1), the photopolymerization initiator (c) in the present invention contains a photopolymerization initiator (c2) having a maximum absorption wavelength of 334 nm or more.

<Photopolymerization initiator (c2)>
The photopolymerization initiator (c2) is a photopolymerization initiator having a maximum absorption wavelength of 334 nm or more.
As described above, by using the photopolymerization initiator (c2) having a maximum absorption wavelength of 334 nm or more in addition to the photopolymerization initiator (c1), it is considered that the light wavelength range that can be effectively used is widened and the sensitivity is improved. Be done.

The maximum absorption wavelength of the photopolymerization initiator (c2) is not particularly limited as long as it is 334 nm or more, but from the viewpoint of sensitivity, it is preferably 335 nm or more, more preferably 336 nm or more, further preferably 338 nm or more, and more preferably 340 nm or more. More preferably, 345 nm or more is particularly preferable, 350 nm or more is most preferable, 390 nm or less is preferable, 380 nm or less is more preferable, 375 nm or less is further preferable, and 370 nm or less is particularly preferable. When the maximum absorption wavelength of the photopolymerization initiator (c2) is set to the lower limit value or more, the internal curing tends to be high, and when the maximum absorption wavelength is set to the upper limit value or less, the sensitivity tends to be high.
Further, the difference in the maximum absorption wavelength between the photopolymerization initiator (c2) and the photopolymerization initiator (c1) is preferably 5 nm or more, more preferably 10 nm or more, further preferably 20 nm or more, particularly preferably 30 nm or more, and further. 60 nm or less is preferable, 50 nm or less is more preferable, 40 nm or less is further preferable, and a combination of a photopolymerization initiator (c1) and a photopolymerization initiator (c2) having an appropriate maximum absorption wavelength may be selected and used. By setting the difference between the maximum absorption wavelengths of the photopolymerization initiator (c1) and the photopolymerization initiator (c2) to be equal to or greater than the lower limit, the range of light wavelengths that can be effectively used tends to be widened and the sensitivity tends to be increased. Therefore, the sensitivity of UV light to i-ray (365 nm) tends to be high.

The chemical structure of the photopolymerization initiator (c2) is not particularly limited, but from the viewpoint of sensitivity, it is preferably an oxime ester-based photopolymerization initiator, and in particular, a photopolymerization initiator having a fluorene skeleton or a carbazole skeleton. Is preferable. In addition, having a fluorene skeleton or a carbazole skeleton means having a fluorene ring or a carbazole ring in the molecular structure, and those rings may be substituted.
Further, from the viewpoint of surface curability, the photopolymerization initiator (c2) is preferably a photopolymerization initiator represented by the following general formula (II).

In formula (II), R ⁷ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ⁸ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
p represents 0 or 1.
R ⁹ represents any monovalent substituent. q represents an integer of 0 to 3.
X represents −N (R ¹⁰ ) − or −C (R ¹¹ ) (R ¹² ) −.
R ^{10 to} R ¹² each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R ¹¹ and R ¹² may be coupled to each other to form a ring.

(R ⁷ )
In the formula (II), R ⁷ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
The alkyl group in R ⁷ may be linear, branched, cyclic, or bonded to each other. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 10 or less, more preferably 7 or less, still more preferably 5 or less, particularly preferably 3 or less, most preferably 2 or less, and usually 1 or more. By setting the number of carbon atoms of the alkyl group to the upper limit or less, the crosslink density tends to increase.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group and the like. Among these, from the viewpoint of sensitivity, a methyl group, an ethyl group, a propyl group, or a butyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is further preferable.
Substituents that the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, and I. Examples thereof include halogen atoms and hydroxyl groups such as, and from the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.

The aromatic ring group in R ^7, and an aromatic hydrocarbon ring group and aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, still more preferably 8 or less. When the number of carbon atoms of the aromatic ring group is at least the above lower limit value, the molecule tends to be stable, and when it is at least the above upper limit value, the solvent solubility tends to be good.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have one free atomic value. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free atomic value. Ring, Pyrolobymidazole ring, Pyrrolopyrazole ring, Pyrrolopyrrole ring, Thienopyrrole ring, Thienothiophene ring, Flopyrole ring, Flofran ring, Thienofranc ring, Benzoisoxazole ring, Benzoisothiazole ring, Benzimidazole ring, Pyridine ring, Pyrazine ring, Examples thereof include pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, sinoline rings, quinoxalin rings, phenanthridin rings, benzimidazole rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings.
Among these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having one free valence is preferable, and a benzene ring having one free valence is more preferable.

Substituents that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, and I. Examples thereof include a halogen atom such as, a hydroxyl group and a nitro group, and from the viewpoint of solvent solubility, an alkoxy group or a hydroxyl group having 1 to 3 carbon atoms is preferable.

From the viewpoint of sensitivity Among these, it is preferred that R ⁷ is an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, further a methyl group or an ethyl group It is preferable, and it is particularly preferable that it is a methyl group.

^(R 8)
In the formula (II), R ⁸ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
The alkyl group in R ⁸ can be linear, even branched, be cyclic, may be one to which they are attached, but solvent solubility viewpoint from straight or branched is preferred, branched and more preferable. On the other hand, from the viewpoint of sensitivity, a group in which a linear alkyl group and a cyclic alkyl group are bonded is preferable.

The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, still more preferably 5 or more, particularly preferably 6 or more, and most preferably 7 or more. Further, it is preferably 12 or less, more preferably 10 or less, still more preferably 9 or less, and particularly preferably 8 or less. When the number of carbon atoms of the alkyl group is at least the above lower limit value, the solvent solubility tends to be good, and when it is at least the above upper limit value, the sensitivity tends to be high.

Substituents that the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. Examples thereof include a carbonyl group, a halogen atom such as F, Cl, Br, and I, a hydroxyl group, and the like, and from the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group and a cyclopentylmethyl group. Cyclopentylethyl group, cyclohexylmethyl group, cyclohexylethyl group and the like can be mentioned. Among these, an isopentyl group, a cyclohexylmethyl group, a cyclopentylethyl group, or a cyclohexylethyl group is preferable, a cyclopentylethyl group or a cyclohexylethyl group is more preferable, and a cyclohexylethyl group is further preferable, from the viewpoint of solvent solubility.

The aromatic ring group in R ^8, and an aromatic hydrocarbon ring group and aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, still more preferably 8 or less. When the number of carbon atoms of the aromatic ring group is at least the above lower limit value, the molecule tends to be stable, and when it is at least the above upper limit value, the solvent solubility tends to be good.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have one free atomic value. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free atomic value. Ring, Pyrolobymidazole ring, Pyrrolopyrazole ring, Pyrrolopyrrole ring, Thienopyrrole ring, Thienothiophene ring, Flopyrole ring, Flofran ring, Thienofranc ring, Benzoisoxazole ring, Benzoisothiazole ring, Benzimidazole ring, Pyridine ring, Pyrazine ring, Examples thereof include pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, sinoline rings, quinoxalin rings, phenanthridin rings, benzimidazole rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings.
Among these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having one free valence is preferable, and a benzene ring having one free valence is more preferable.

Substituents that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, and I. Examples thereof include a halogen atom such as, a hydroxyl group and a nitro group, and from the viewpoint of solvent solubility, an alkoxy group or a hydroxyl group having 1 to 5 carbon atoms is preferable. The alkyl chain portion of the substituent may be linear or branched, and further has a substituent such as an alkoxy group having 1 to 3 carbon atoms, an alkylthio group having 1 to 3 carbon atoms, a halogen atom, a hydroxyl group, or a nitro group. You may be doing it.

From the viewpoint of long wavelength of the light absorption wavelength Among these, R ⁸ is preferably substituted is also an aromatic ring group, an aromatic optionally substituted hydrocarbon It is more preferably a ring group.

(P)
In the formula (II), p represents 0 or 1. From the viewpoint of sensitivity, p is preferably 0, while from the viewpoint of solvent solubility, p is preferably 1.

(R ⁹ )
In formula (II), R ⁹ represents any monovalent substituent.
As any monovalent substituent, an alkyl group having 1 to 10 carbon atoms such as a methyl group and an ethyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; F, Cl, Br, I and the like. Halogen atom; acyl group having 1 to 10 carbon atoms; alkyl ester group having 1 to 10 carbon atoms; alkoxycarbonyl group having 1 to 10 carbon atoms; alkyl halide group having 1 to 10 carbon atoms; 4 to 10 carbon atoms Aromatic ring group; amino group; aminoalkyl group having 1 to 10 carbon atoms; hydroxyl group; nitro group; CN group; benzoyl group which may have a substituent; tenoyl group which may have a substituent and the like. Can be mentioned. Examples of the substituent that the benzoyl group or the tenoyl group may have include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and the like, and the group has 0 to 3 carbon atoms. You may. Among these, a nitro group and a 2-tenoyl group are preferable, and a nitro group is more preferable, from the viewpoint of lengthening the absorption wavelength.
In R ^9, when q is 2 or more, may form a ring by combining a plurality of R ⁹ together. The ring may be an aliphatic ring or an aromatic ring.

(Q)
In the formula (II), q represents an integer of 0 to 3. From the viewpoint of radical generation efficiency, it is preferably 0 or 1, and more preferably 1.

(X)
In the formula (II), X represents −N (R ¹⁰ ) − or −C (R ¹¹ ) (R ¹² ) −. Among these, −N (R ¹⁰ ) − is preferable from the viewpoint of sensitivity.

(R ^{10 to} R ¹² )
In the formula (II), R ^{10 to} R ¹² each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

The alkyl groups in R ^{10 to} R ¹² may be linear, branched, cyclic, or bonded thereof, but from the viewpoint of sensitivity, linear or branched is preferable, and linear is preferable. Is more preferable.
The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, particularly preferably 5 or more, and preferably 10 or less, more preferably 8 or less. , More preferably 6 or less, and particularly preferably 4 or less. When the number of carbon atoms of the alkyl group is at least the above lower limit value, the solvent solubility tends to be good, and when it is at least the above upper limit value, the sensitivity tends to be high.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group and a 2-ethylhexyl group. And so on. Among these, from the viewpoint of the balance between sensitivity and solvent solubility, an ethyl group, a propyl group, an isopropyl group, or a butyl group is preferable, an ethyl group or a propyl group is more preferable, and an ethyl group is further preferable.
Substituents that the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, and I. Examples thereof include halogen atoms and hydroxyl groups such as, and from the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.

Examples of the aromatic ring group in R ^{10 to} R ¹² include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, still more preferably 8 or less. When the number of carbon atoms of the aromatic ring group is at least the above lower limit value, the molecule tends to be stable, and when it is at least the above upper limit value, the solvent solubility tends to be good.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have one free atomic value. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free atomic value. Ring, Pyrolobymidazole ring, Pyrrolopyrazole ring, Pyrrolopyrrole ring, Thienopyrrole ring, Thienothiophene ring, Flopyrole ring, Flofran ring, Thienofranc ring, Benzoisoxazole ring, Benzoisothiazole ring, Benzimidazole ring, Pyridine ring, Pyrazine ring, Examples thereof include pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, sinoline rings, quinoxalin rings, phenanthridin rings, benzimidazole rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings. Among these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having one free valence is preferable, and a benzene ring having one free valence is more preferable.

Substituents that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, and I. Examples thereof include a halogen atom such as, a hydroxyl group and a nitro group, and from the viewpoint of solvent solubility, an alkoxy group or a hydroxyl group having 1 to 3 carbon atoms is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.

Further, R ¹¹ and R ¹² may be coupled to each other to form a ring, and the ring may be an aliphatic ring or an aromatic ring.

Among these, from the viewpoint of sensitivity, ^{each of R 10 to} R ¹² is preferably an alkyl group which may independently have a substituent, more preferably an unsubstituted alkyl group, and R ¹⁰ is It is more preferably a methyl group or an ethyl group, ^{and it is more preferable that R 11} and R ^{12 are butyl groups.}

Commercially available products of the photopolymerization initiator (c2) include OXE-02 manufactured by BASF, TR-PBG-304, TR-PBG-314, and TR-PBG-358 manufactured by Changzhou Powerful Electronics New Materials Co., Ltd. Can be mentioned. Further, those described in Japanese Patent No. 4223071, those described in International Publication No. 2016/010036, and those described in Japanese Patent No. 5682094 can also be used.

Specific examples of the photopolymerization initiator (c2) include the following. In the formula, nBu represents a normal butyl group.

(C) The photopolymerization initiator may further contain other photopolymerization initiators other than the photopolymerization initiator (c1) and the photopolymerization initiator (c2).
Examples of other photopolymerization initiators include metallocene compounds containing the titanosen compounds described in JP-A-59-152396 and JP-A-61-151197 of Japan; Japanese Patent Laid-Open No. 2000-56118. Hexaaryl-biimidazole derivative described in Japanese Patent Application Laid-Open No. 10-39503; N-aryl-α-amino acids such as halomethylated oxadiazole derivative, halomethyl-s-triazine derivative, N-phenylglycine and the like described in Japanese Patent Application Laid-Open No. 10-39503. , N-aryl-α-amino acid salts, radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; Examples thereof include oxime ester derivatives described in Japanese publications.

Specifically, for example, as titanosen derivatives, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro) Pheni-1-yl), Dicyclopentadienyl Titanium Bis (2,3,5,6-Tetrafluoropheni-1-yl), Dicyclopentadienyl Titanium Bis (2,4,6-Trifluorophenyl) 1-yl), Dicyclopentadienyl Titanium Di (2,6-difluoropheni-1-yl), Dicyclopentadienyl Titanium Di (2,4-difluoropheni-1-yl), Di (Methylcyclopenta) Dienyl) Titanium Bis (2,3,4,5,6-pentafluoropheni-1-yl), Di (Methylcyclopentadienyl) Titanium Bis (2,6-difluoropheni-1-yl), Dicyclo Examples thereof include pentadienyl titanium [2,6-di-fluoro-3- (pyro-1-yl) -pheni-1-yl].

Examples of the biimidazole derivatives include 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole. Dimeric, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxy) Phenyl) -4,5-diphenylimidazole dimer and the like can be mentioned.

Examples of the halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole and 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 can be mentioned.

Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and 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 can be mentioned.

Examples of α-aminoalkylphenone derivatives include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4). -Morphorinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzo Aet, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- ( Examples thereof include 4-diethylaminobenzoyl) coumarin and 4- (diethylamino) chalcone.

Examples of the oxime ester derivative include Japanese Patent Laid-Open No. 2004-534797, Japanese Patent Application Laid-Open No. 2000-80068, Japanese Patent Application Laid-Open No. 2006-36750, Japanese Patent Application Laid-Open No. 2008-179611, and Japanese Patent Laid-Open No. 2004-179611. Examples thereof include oxime ester compounds described in Japanese Patent Publication No. 2012-526185, Japanese Patent Laid-Open No. 2012-591191 and the like. Among them, from the viewpoint of sensitivity, 4-acetoxyimino-5- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -5-methyloxopentanoate is also used as a product name, OXE-. 01 (manufactured by BASF), TR-PBG-305 (manufactured by Changzhou Power Co., Ltd.), NCI-930 (manufactured by ADEKA) and the like can be mentioned as preferable ones.
The above-mentioned other photopolymerization initiators may be used alone or in combination of two or more.

<Sensitizer>
If necessary, the photopolymerization initiator may be used in combination with a sensitizing dye according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. Examples of these sensitizing dyes include xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958, Japanese Patent Application Laid-Open No. 4-219756, Japanese Patent Application Laid-Open No. 3-239703, and Japanese Patent Application Laid-Open No. 5-289335. A coumarin dye having a heterocycle described in Japanese Patent Application Laid-Open No. 3-239703, a 3-ketocoumarin compound described in Japanese Patent Application Laid-Open No. 5-289335, etc., Japanese Patent Application Laid-Open No. 6-19240. Japanese Patent Application Laid-Open No. 47-2528, Japanese Patent Application Laid-Open No. 54-155292, Japanese Patent Application Laid-Open No. 45-373777, Japanese Patent Application Laid-Open No. 48-84183. , Japanese Patent Application Laid-Open No. 52-112681, Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88805, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2 The dialkyl described in Japanese Patent Application Laid-Open No. -69, Japanese Patent Application Laid-Open No. 57-168888, Japanese Patent Application Laid-Open No. 5-107761, Japanese Patent Application Laid-Open No. 5-210240, Japanese Patent Application Laid-Open No. 4-288818, etc. Examples thereof include dyes having an aminobenzene skeleton.

Of these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone. , 3,4-Diaminobenzophenone and other benzophenone compounds; 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-Thiadiazol, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, ( It is a p-dialkylaminophenyl group-containing compound such as p-diethylaminophenyl) pyrimidine.
The most preferable of these is 4,4'-dialkylaminobenzophenone.
The sensitizing dye may also be used alone or in combination of two or more.

(C) The content ratio of the photopolymerization initiator is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, based on the total solid content of the photosensitive resin composition of the present invention. More preferably 3% by mass or more, particularly 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, still more. It is preferably 8% by mass or less, and particularly preferably 6% by mass or less. (C) The effect of oxygen inhibition tends to be suppressed by setting the content ratio of the photopolymerization initiator to be equal to or higher than the lower limit value, and the substrate adhesion tends to be improved by setting the content ratio to be lower than the upper limit value. ..

(C) The content ratio of the photopolymerization initiator (c1) in the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 10% by mass or more, 20. More preferably, it is more preferably mass% or more, particularly preferably 30% by mass or more, most preferably 40% by mass or more, and further preferably 99.9% by mass or less, more preferably 99% by mass or less, still more preferably 90% by mass or less. , 60% by mass or less is most preferable. When the content ratio of the photopolymerization initiator (c1) is at least the above lower limit value, the internal curability tends to be good, and when it is at least the above upper limit value, the curability of the top portion of the pattern is good. Tends to be.

(C) The content ratio of the photopolymerization initiator (c2) in the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 10% by mass or more, and 40. The mass% or more is the most preferable, and 99.9% by mass or less is preferable, 99% by mass or less is more preferable, 90% by mass or less is further preferable, 80% by mass or less is further preferable, and 60% by mass or less is particularly preferable. .. When the content ratio of the photopolymerization initiator (c2) is at least the above lower limit value, the curability of the top portion of the pattern tends to be good, and when it is at least the above upper limit value, the internal curability is good. Tends to be.

<(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 such that the solubility of the exposed portion and the non-exposed portion in the alkali developing solution changes after the coating film obtained by applying and drying the photosensitive resin composition is exposed. Although not limited, an alkali-soluble resin having an acidic functional group such as a hydroxyl group, a carboxyl group, a phosphoric acid group, or a sulfonic acid group is preferable, and an alkali-soluble resin having a carboxyl group is more preferable. Further, those having an ethylenically unsaturated group are preferable from the viewpoint of curability, and an alkali-soluble resin having an ethylenically unsaturated group and a carboxyl group is more preferable from the viewpoint of curability and developability. Specific examples thereof include an epoxy (meth) acrylate resin having a carboxyl group and an acrylic copolymer resin, and more specific examples thereof are (A1-1), (A1-2) and (A2-) described later. 1), (A2-2), (A2-3) and (A2-4) are mentioned, and these may use one kind or two or more kinds. Among the above, epoxy (meth) acrylate resins (A1-1) and (A1-2) having a carboxyl group are particularly desirable.

The epoxy (meth) acrylate resin having a carboxyl group is a reaction product of the epoxy resin and an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety. It is a resin obtained by further reacting a hydroxyl group generated in the reaction with a polybasic acid and / or an anhydride thereof. Further, before reacting the polybasic acid and / or its anhydride with a hydroxyl group, a compound having two or more substituents capable of reacting with the hydroxyl group is reacted, and then the polybasic acid and / or its anhydride is added. The resin obtained by the reaction is also included in the epoxy (meth) acrylate resin. Further, a resin obtained by reacting the carboxyl group of the resin obtained by the above reaction with a compound having a functional group capable of further reacting is also included in the epoxy (meth) acrylate resin.
As described above, the epoxy (meth) acrylate resin has substantially no epoxy group due to its chemical structure and is not limited to "(meth) acrylate", but the epoxy resin is a raw material and is not limited to "(meth) acrylate". Since "(meth) acrylate" is a typical example, it is named in this way according to the convention.

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)>
It was obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting with a polybasic acid and / or its anhydride. Alkaline-soluble resin.
<Epoxy (meth) acrylate resin (A1-2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to the epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or its anhydride. The alkali-soluble resin obtained by this.

<Epoxy (meth) acrylate resin (A1-1)>
The epoxy resin as a raw material includes a raw material compound before forming the resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins and used. Further, as the epoxy resin, a compound obtained by reacting a phenolic compound with epihalohydrin can be used. The phenolic compound is preferably a compound having a divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
The types of epoxy resin include cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, biphenyl novolac type epoxy resin, naphthalene novolac type epoxy resin, and so on. An epoxy resin, an adamantyl group-containing epoxy resin, a fluorene-type epoxy resin, or the like, which is a reaction product of a polyaddition reaction product of dicyclopentadiene with phenol or cresol and epihalohydrin, can be preferably used. Those having an aromatic ring can be preferably used.
Specific examples of the epoxy resin include bisphenol A type epoxy resin (for example, "jER (registered trademark; the same applies hereinafter) 828", "jER1001", "jER1002", "jER1004", etc.) manufactured by Mitsubishi Chemical Corporation, bisphenol A. Epoxy obtained by the reaction of the alcoholic hydroxyl group of the type epoxy resin with epichlorohydrin (for example, "NER-1302" (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin (for example, Mitsubishi Chemical) "JER807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Mitsubishi Chemical Corporation), an epoxy resin obtained by the reaction of an alcoholic hydroxyl group of a bisphenol F type epoxy resin with epichlorohydrin (for example, Japan "NER-7406" manufactured by Yakusha (epoxy equivalent 350, softening point 66 ° C), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (For example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Corporation), (o, m, p. -) Cresol novolak type epoxy resin (for example, "EOCN (registered trademark. The same shall apply hereinafter) -102S", "EOCN-1020", "EOCN-1020") manufactured by Nippon Kayaku Co., Ltd., triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Corporation), Trisphenol methane type epoxy resin (for example, "EPPN (registered trademark; the same applies hereinafter) -501", "EPPN-502", "EPPN-502" manufactured by Nippon Kayaku Co., Ltd. EPPN-503 "), alicyclic epoxy resin ("Seroxide (registered trademark; the same shall apply hereinafter) 2021P "manufactured by Daicel Co., Ltd." A resin (for example, "EXA-7200" manufactured by DIC, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), an epoxy resin represented by the following general formulas (a1) to (a5), and the like are preferably used. Can be done. Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (a1), and "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (a2). Examples of the epoxy resin represented by the following general formula (a4) include "NC-3000" and "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Corporation.

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

In the above general formula (a2), b12 indicates an average value and indicates a number of 0 to 10. R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. The plurality of R ^21s existing in one molecule may be the same or different from each other.

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

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

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

In the above general formula (a5), R ^{51 to} R ⁵⁴ are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms. R ⁵⁵ is 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, and R ⁵⁶ is an alkylene group having 1 to 5 carbon atoms independently. Is. k is an integer of 1 to 5, l is an integer of 0 to 13, and m is an integer of 0 to 5 independently.
Among these, it is preferable to use the epoxy resin represented by any of the general formulas (a1) to (a5).

Examples of the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m-, p-vinyl benzoic acid, and (meth). ) Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, cyano-substituted acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( Meta) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- ( Meta) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) ) Acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) Acryloyloxybutylmaleic acid,
The (meth) acrylic acid ester is a single amount having one hydroxyl group at the end by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to (meth) acrylic acid. Body and
Alternatively, a monomer having one hydroxyl group at the terminal such as hydroxyalkyl (meth) acrylate, or a compound having one hydroxyl group at the terminal such as pentaerythritol tri (meth) acrylate, and (maleic) succinic acid, Examples thereof include (meth) acrylic acid esters having one or more ethylene unsaturated groups and one carboxyl group at the end by adding an acid (anhydride) such as (anhydrous) phthalic acid and (maleic anhydride) maleic acid. .. In addition, (meth) acrylic acid dimer and the like can also be mentioned.

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

As the epoxy resin, α, β-unsaturated monocarboxylic acid, α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst, one type may be used alone, or two types may be used. The above may be used together.
The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin. , More preferably in the range of 0.7 to 1.1 equivalents.
When the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group used is equal to or higher than the above lower limit, the amount of unsaturated group introduced becomes sufficient, and the subsequent polybasic acid and subsequent polybasic acid and / Or the reaction with the anhydride thereof is sufficient, and there is a tendency that the residual epoxy group can be suppressed. On the other hand, when the amount used is not more than the upper limit, α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted product and the curing characteristics deteriorate. Tends to be able to suppress.

Polybasic acid and / or its anhydrate include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid and methylhexahydrophthalic acid. Examples thereof include one or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

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

A known method can also be used for the addition reaction of polybasic acid and / or its anhydride, and α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid having a carboxyl group to an epoxy resin can be used. The desired product can be obtained by a continuous reaction under the same conditions as the addition reaction of the ester. The addition amount of the polybasic acid and / or its anhydride component is preferably such that the acid value of the produced carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mgKOH / g, and further 20 It is preferably in the range of ~ 140 mgKOH / g. When the acid value of the carboxyl group-containing epoxy (meth) acrylate resin is at least the above lower limit value, the alkali developability tends to be good, and when it is at least the above upper limit value, the curability tends to be good.

<Synthesis of (A1-1) resin and synthesis of (A1-2) resin in which a polyhydric alcohol is added to (A1-1) resin to introduce a branched structure>
Assuming that a polyhydric alcohol such as trimethylolpropane, pentaerythritol, or dipentaerythritol was added during the addition reaction synthesis of the polybasic acid and / or its anhydride of the above (A1-1) resin to introduce a multi-branched structure. May be good.
A carboxyl group-containing epoxy (meth) acrylate resin is usually a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and a polybasic acid and a polybasic acid. / Or after mixing the anhydride thereof, or after mixing the epoxy resin with α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group, polybasic acid and / or Alternatively, it can be obtained by mixing an anhydride thereof and a polyvalent alcohol and then heating the mixture. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyhydric alcohol is not particularly limited. Any hydroxyl group present in the mixture of the reaction product of the epoxy resin and the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group and the polyhydric alcohol by heating. A polybasic acid and / or its anhydride undergoes an addition reaction with respect to.

As the carboxyl group-containing epoxy (meth) acrylate resin, one type may be used alone, or two or more types of resins may be mixed and used.
From the viewpoint that the amount of polyhydric alcohol used is effective while suppressing thickening and gelation, the epoxy resin component and α, β-unsaturated monocarboxylic acid or α, β- having a carboxyl group in the ester moiety It is usually about 0.01 to 0.5 times by mass, preferably about 0.02 to 0.2 times by mass with respect to the reaction product with the unsaturated monocarboxylic acid ester component.

The acid values of the epoxy (meth) acrylate resins (A1-1) and (A1-2) thus obtained are usually 10 mgKOH / g or more, preferably 50 mgKOH / g or more, more preferably 70 mgKOH / g or more, and further. It is preferably 90 mgKOH / g or more, preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, still more preferably 120 mgKOH / g or less. When the acid value of the resin is at least the lower limit value, the developability tends to be good, and when it is at least the upper limit value, the alkali resistance tends to be good.

The polystyrene-equivalent weight average molecular weight (Mw) of the epoxy (meth) acrylate resins (A1-1) and (A1-2) measured by gel permeation chromatography (GPC) is preferably 1,000 or more. , 500 or more is more preferable. Further, it is preferably 20,000 or less, more preferably 15,000 or less, further preferably 10,000 or less, further preferably 8,000 or less, and 6,000 or less. Is particularly preferable. When the weight average molecular weight (Mw) is at least the above lower limit value, the sensitivity, coating film strength, and alkali resistance tend to be good, and when it is at least the above upper limit value, the developability and resolubility are good. Tend to be able to.

<Acrylic copolymer resin (A2-1), (A2-2), (A2-3), (A2-4)>
Examples of the acrylic copolymer resin include Japanese Patent Laid-Open No. 7-2072111, Japanese Patent Application Laid-Open No. 8-259876, Japanese Patent Application Laid-Open No. 10-300922, Japanese Patent Application Laid-Open No. 11-140144, Japan. Various highs described in Japanese Patent Laid-Open Nos. 11-174224, Japanese Patent Laid-Open Nos. 2000-56118, Japanese Patent Laid-Open Nos. 2003-233179, Japanese Patent Laid-Open No. 2007-270147, etc. Although molecular compounds can be used, the following resins (A2-1) to (A2-4) are preferable, and (A2-1) resin is particularly preferable.

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

From the viewpoint of sensitivity, the photosensitive resin composition of the present invention is an alkali-soluble resin containing an ethylenically unsaturated group (A1-1), (A1-2), (A2-1), (A2-3). It is more preferable to include at least one of the above. From the viewpoint of surface curability, the photosensitive resin composition of the present invention is an epoxy (meth) acrylate resin as an alkali-soluble resin containing an ethylenically unsaturated group, at least of (A1-1) and (A1-2). It is particularly preferable to include any of them.

The photosensitive resin composition of the present invention may be used in combination with other alkali-soluble resins.
The other alkali-soluble resins are not limited, and may be selected from the resins usually used in the photosensitive resin composition for color filters. For example, the alkali-soluble resins described in Japanese Patent Application Laid-Open No. 2007-271727, Japanese Patent Application Laid-Open No. 2007-316620, Japanese Patent Application Laid-Open No. 2007-334290 and the like can be mentioned.

(A) The content ratio 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, still more preferably, with respect to the total solid content of the photosensitive resin composition of the present invention. Is 20% by mass or more, usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less. (A) When the content ratio of the alkali-soluble resin is at least the above lower limit value, the solubility of the unexposed part in the developing solution tends to be good, and when it is at least the above upper limit value, the development to the exposed part tends to be good. Excessive penetration of the liquid can be suppressed, and the image tends to be sharpened and the adhesion tends to be good.
As described above, the photosensitive resin composition of the present invention is (a) an alkali-soluble resin as described above (A1-1), (A1-2), (A2-1), (A2-2). , (A2-3) and (A2-4) are preferably contained, and when other alkali-soluble resins are contained, the content ratio thereof is 20 mass with respect to the total of (a) alkali-soluble resins. % Or less, preferably 10% by mass or less.

<(B) Photopolymerizable monomer>
The photosensitive resin composition of the present invention contains (b) a photopolymerizable monomer from the viewpoint of sensitivity and the like.
Examples of the (b) photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter, may be referred to as “ethylenic monomer”). .. Specific examples thereof include (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, and an ester of a polyvalent or monovalent alcohol. ..

In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is usually 2 or more, preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, particularly preferably 6 or more, and usually 10 or less, preferably 10 or less. It is 8 or less. When the number of ethylenically unsaturated groups is at least the above lower limit value, the photosensitive resin composition tends to have high sensitivity, and when it is at least the above upper limit value, the curing shrinkage during polymerization tends to be small. be.
Examples of the polyfunctional ethylenic monomer include, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, an aromatic poly. Examples thereof include an ester obtained by an esterification reaction between a polyvalent hydroxy compound such as a hydroxy compound and an unsaturated carboxylic acid and a polybasic carboxylic acid.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propanetriacrylate, trimethylol ethanetriacrylate, pentaerythritol diacrylate, and 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 in which the acrylates of these exemplary compounds are replaced with methacrylates. Similarly, an itaconic acid ester replaced with itaconate, a crotonic acid ester replaced with clonate, a maleic acid ester replaced with maleate, and the like can be mentioned.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcindiacrylate, resorcindimethacrylate, and pyrogalloltriacrylate. And so on.
The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single substance, but typical specific examples include acrylic acid, phthalic acid, and Examples thereof include a condensate of ethylene glycol, a condensate of acrylic acid, maleic acid and diethylene glycol, a condensate of methacrylic acid, terephthalic acid and pentaerythritol, a condensate of acrylic acid, adipic acid, butanediol and glycerin.

In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound is reacted with a hydroxyl group-containing (meth) acrylic acid ester or a polyisocyanate compound is reacted with a polyol and a hydroxyl group-containing (meth) acrylic acid ester. Urethane (meth) acrylates as obtained; epoxy acrylates such as an addition reaction product of a polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate. Allyl esters such as; vinyl group-containing compounds such as divinyl phthalate are useful.
These may be used alone or in combination of two or more.

(B) The content ratio of the photopolymerizable monomer is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 30 with respect to the total solid content of the photosensitive resin composition. It is 0% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. When the content of the photopolymerizable monomer is not more than the above upper limit value, the permeability of the developing solution to the exposed portion becomes appropriate, and a good image tends to be obtained. (B) The lower limit of the content of the photopolymerizable monomer is usually 1% by mass or more, preferably 5% by mass or more. When it is at least the above lower limit value, the photocuring due to ultraviolet irradiation is improved and the alkali developability tends to be good.

The mass ratio of (a) the content ratio of the alkali-soluble resin to the content ratio of (b) the photopolymerizable monomer in the photosensitive resin composition of the present invention is usually 0.5 or more, preferably 1 or more, more preferably 2 or more. It is more preferably 2.5 or more, and usually 15 or less, preferably 10 or less, more preferably 8 or less, still more preferably 5 or less. When it is at least the above lower limit value, the curing shrinkage at the time of curing tends to be small, and when it is at least the above upper limit value, the hardness of the cured film tends to be high.

<(D) Color material>
The photosensitive resin composition of the present invention contains a coloring material when used for forming pixels of a color filter, a black matrix, a colored spacer, and the like. The coloring material refers to a material that colors the photosensitive resin composition of the present invention. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like.

As the pigment, pigments of various colors such as blue pigment, green pigment, red pigment, yellow pigment, purple pigment, orange pigment, brown pigment and black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolenone, dioxazine, indanthrone, and perylene, various inorganic pigments can be used as the structure. Is.

Specific examples of pigments that can be used in the present invention are shown below by pigment numbers. The terms such as "CI Pigment Red 2" listed below mean the color index (CI).
As the 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 can be mentioned. Among these, preferably 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 can be mentioned.

As the 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, preferably 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 can be mentioned.
Examples of the green pigment include C.I. I. Pigment Greens 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 can be mentioned. Among these, preferably C.I. I. Pigment Greens 7, 36 and 58 can be mentioned.

As the 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, preferably 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 the 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, preferably, C.I. I. Pigment Oranges 38 and 71 can be mentioned.

As the 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, preferably C.I. I. Pigment Violet 19, 23, more preferably C.I. I. Pigment Violet 23 can be mentioned.

When the photosensitive resin composition of the present invention is a photosensitive resin composition for a resin black matrix of a color filter, a black coloring material can be used as the (d) coloring material. The black color material may be a black color material alone or a mixture of red, green, blue and the like. Further, these coloring materials can be appropriately selected from inorganic or organic pigments and dyes.
Coloring materials that can be mixed and used to prepare black coloring materials include Victoria Pure Blue (42595), Auramine O (41000), Cachilon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). , Safranin OK70: 100 (50240), Eriograusin X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Simler First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Simler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fastgen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionol Gen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (Note that the numbers in () above mean the color index (CI)).

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

Examples of the black color material 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.
When a black color material is used among these (d) color materials, carbon black is preferable from the viewpoint of light shielding rate and image characteristics. Examples of carbon black include the following carbon blacks.

Made by 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
Made by Degusa: Printex (registered trademark; the same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexA, PrintexA. 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
Made by Cabot Corporation: Monarch (registered trademark; the same shall apply hereinafter) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark; same as REGAL). REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN® XC72R, ELFTEX®-8
Made by Biller: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN10URA RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

As an example of other black pigments, titanium black, aniline black, iron oxide-based black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments.

Further, as the pigment, barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, chromium oxide and the like can also be used. A plurality of these various pigments can be used in combination. For example, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a purple pigment can be used in combination for adjusting the chromaticity.

The average particle size of the pigment used in the present invention may be any as long as it can develop a desired color when used as a colored layer of a color filter, and is not particularly limited and varies depending on the type of pigment used. It is preferably in the range of ~ 100 nm, and more preferably in the range of 10 to 70 nm. When the average particle size of the pigment is in the above range, the color characteristics of the liquid crystal display device manufactured by using the photosensitive resin composition of the present invention tend to be high quality.
When the pigment is carbon black, the average particle size is preferably 60 nm or less, more preferably 50 nm or less, and more preferably 20 nm or more. By setting the average particle size to the upper limit or less, the scattering becomes small, and there is a tendency that deterioration of color characteristics such as light-shielding property and contrast can be suppressed. Further, by setting the average particle size to the lower limit value or more, the amount of the dispersant does not need to be excessively large, and the dispersibility tends to be good.
The average particle size of the pigment can be obtained by a method of directly measuring the size of the primary particles from an electron micrograph. Specifically, the minor axis diameter and the major axis diameter of each primary particle are measured, and the average thereof is taken as the particle size of the particle. Next, for 100 or more particles, the volume (mass) of each particle is obtained by approximating it to a rectangular parallelepiped having the obtained particle size, and the volume average particle size is obtained and used as the average particle size. The same result can be obtained regardless of whether the electron microscope is a transmission type (TEM) or a scanning type (SEM).

Further, the photosensitive resin composition of the present invention preferably contains at least a pigment, but in addition, a dye may be used in combination as long as the effect of the present invention is not affected. Examples of dyes that can be used in combination include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

Examples of the azo dye 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. Moldant Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples include Moldant Black 7.

Examples of the anthraquinone dye 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 can be used as quinoneimine dyes, for example, C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are used as 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 can be used as nitro dyes, for example, C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like can be mentioned.

(D) The content ratio of the coloring material can be usually selected in the range of 1 to 70% by mass with respect to the total solid content in the photosensitive resin composition. Within this range, 20% by mass or more is more preferable, 30% by mass or more is further preferable, 40% by mass or more is particularly preferable, and 60% by mass or less is more preferable.

The photosensitive resin composition of the present invention can be used for various purposes as described above, but the excellent image forming property is particularly effective when used for forming a black matrix for a color filter. .. When used to form a black matrix, (d) use a black color material such as carbon black or titanium black described above, or mix multiple types of color materials other than black and adjust to black. Just do it. Among them, it is particularly preferable to use carbon black from the viewpoint of dispersion stability and light-shielding property.

The present invention is particularly effective in the region where the pigment concentration of the black pigment is high. Especially in recent years, it is necessary to increase the concentration of black pigment in order to increase the degree of shading. The content ratio of the black pigment in the region where the effect is large is 40% by mass or more, preferably 45% by mass or more, and more preferably 50% by mass or more, based on the total solid content of the photosensitive resin composition. Is more preferable.

When the content ratio of the black pigment in the photosensitive resin composition is within the above range, a photosensitive resin composition having a high light-shielding property (optical density, OD value) can be obtained. Specifically, by setting the content of the black pigment to 45% by mass or more, the optical density when a black matrix having a thickness of 1 μm is formed using the photosensitive resin composition of the present invention is 4.0 or more. Can be a value. The optical density is more preferably 4.2 or more. In a region with high light-shielding properties, ultraviolet rays are difficult to penetrate deeply, and cross-linking due to photopolymerization is weakened especially in the portion where the substrate and the fine wire are in close contact. However, when the photosensitive resin composition of the present invention is used, the black pigment is particularly weak. When the content ratio of the above is large, the effect of the present invention can be confirmed well. As the content ratio of the black pigment, 40 to 65% by mass is particularly effective. By setting the content ratio of the black pigment to the lower limit value or more, it tends to be possible to suppress the film thickness from becoming too large with respect to the color density, and by setting it to the upper limit value or less, it is easy to secure sufficient image formability. Tend.

In the photosensitive resin composition, the content ratio of (d) the coloring material is (a) 20 parts by mass or more, preferably 30 parts by mass or more, and more preferably 40 parts by mass or more per 100 parts by mass of the alkali-soluble resin. More preferably 60 parts by mass or more, further preferably 80 parts by mass or more, particularly preferably 120 parts by mass or more, most preferably 160 parts by mass or more, and usually 500 parts by mass or less, preferably 300 parts by mass or less. It is preferably 280 parts by mass or less. (D) When the content ratio of the coloring material is at least the above lower limit value, it tends to be easy to suppress the decrease in solubility of the unexposed portion in the developing solution, and when it is at least the above upper limit value, the desired image film is formed. The thickness tends to be easy to obtain.

<(E) Dispersant>
In the present invention, it is important to finely disperse the coloring material and stabilize the dispersed state thereof in order to ensure the stability of quality. Therefore, it is preferable to include (e) a dispersant.
As the dispersant, a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or these groups; a primary, secondary or tertiary amino group. A quaternary ammonium base; a polymer dispersant having a functional group such as a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is preferable. Among them, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine is particularly preferable. By using a polymer dispersant having these basic functional groups, the dispersibility can be improved and a high light-shielding property tends to be achieved.

Examples of the polymer dispersant include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants consisting of monomers having amino groups and macromonomers, and polyoxyethylene alkyl ether-based agents. Examples thereof include dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

Specific examples of such a dispersant include EFKA (registered trademark, manufactured by EFKA), Disperbyk (registered trademark, manufactured by Big Chemie), and Disparon (registered trademark, manufactured by Kusumoto Kasei) under the trade names. 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.), Azisper (registered trademark, manufactured by Ajinomoto Fine Techno). .) Etc. can be mentioned.
These polymer dispersants may be used alone or in combination of two or more.

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

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less, and more preferably 30,000 or less. .. By setting the weight average molecular weight (Mw) to the upper limit or less, the alkali developability tends to be good even when the pigment concentration is high.
Examples of the urethane-based and acrylic-based polymer dispersants include DISPERBYK-160 to 167, 182 series (all urethane-based), DISPERBYK-2000, 2001 (all acrylic-based) (all manufactured by Big Chemie). .. DISPERBYK-167, 182 and the like are particularly preferable urethane-based polymer dispersants having the above-mentioned basic functional groups and having polyester and / or polyether bonds and having a weight average molecular weight of 30,000 or less.

<Urethane-based polymer dispersant>
To specifically exemplify a preferable chemical structure as a urethane-based polymer dispersant, for example, it is the same as a polyisocyanate compound and a compound having one or two hydroxyl groups in the molecule and having a number average molecular weight of 300 to 10,000. Examples thereof include a dispersed resin having a weight average molecular weight of 1,000 to 200,000, which is obtained by reacting an active hydrogen with a compound having a tertiary amino group in the molecule.

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, trizine diisocyanate and the like. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanate such as dimerate diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), ω, ω Alicyclic diisocyanate such as ′-diisocinatedimethylcyclohexane, aliphatic diisocyanate having aromatic ring such as xylylene diisocyanate, α, α, α ′, α ′-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1, 6,11-Undecantriisocyanate, 1,8-diisocyanate-4-isocyanatemethyloctane, 1,3,6-hexamethylenetriisocyanate, bicycloheptantriisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate Such as triisocyanates, trimerics thereof, water adducts, and polyol adducts thereof. The polyisocyanate is preferably a trimer of organic diisocyanate, and most preferably a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.

As a method for producing an isocyanate trimer, the polyisocyanate is subjected to an isocyanate group moiety using an appropriate trimerization catalyst such as tertiary amines, phosphins, alkoxides, metal oxides, carboxylates and the like. A method of obtaining a desired isocyanurate group-containing polyisocyanate by performing a trimerization, stopping the trimerization by adding a catalytic poison, and then removing the unreacted polyisocyanate by solvent extraction and thin film distillation.

As a compound having one or two hydroxyl groups in the same molecule and having an average molecular weight of 300 to 10,000, polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and one-terminal hydroxyl group of these compounds have the number of carbon atoms. Examples thereof include those alkenylated with 1 to 25 alkyl groups and mixtures of two or more of these.

Examples of the polyether glycol include a polyether diol, a polyether ester diol, and a mixture of two or more of these. Polyether diols are obtained by using alkylene oxide alone or in copolymerization, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and them. A mixture of two or more of the above can be mentioned.

Polyester ester diols are 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, such as poly (poly). Oxytetramethylene) adipate and the like. The most preferable polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Examples of 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, etc.). 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-Glycoldiol, 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 alicyclic glycols, xyl It is obtained by polycondensing with aromatic glycol such as len glycol, bishydroxyethoxybenzene, N-alkyldialkanolamine such as N-methyldiethanolamine), for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate. Polylactone diols or polylactone monools obtained by using the above diols or monovalent alcohols having 1 to 25 carbon atoms as an initiator, such as polyethylene / propylene adipate, for example, polycaprolactone glycols, polymethylvalerolactones and the like. Examples include a mixture of two or more. The most preferable polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator.

Polycarbonate glycol includes poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate and the like, and polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol and the like. Can be mentioned.
These may be used alone or in combination of two or more.

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

The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, a heterocyclic structure, and more specifically, an imidazole ring or a triazole ring.
To exemplify such a compound having an active hydrogen and a tertiary amino group in the same molecule, 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-Butandiamine and the like.

When the tertiary amino group has a nitrogen-containing heterocyclic structure, the nitrogen-containing heterocycle includes a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, a benzimidazole ring, and a benzo. Nitrogen-containing hetero 5-membered ring such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiasiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, aclysine ring, isoquinoline ring and other nitrogen-containing hetero 6-membered ring. Ring is mentioned. Of these nitrogen-containing heterocycles, the imidazole ring or the triazole ring is preferable.

Specific examples of these 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 the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole and 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 alone or in combination of two or more.
The preferred blending ratio of the raw materials for producing a urethane-based polymer dispersant is 10 compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound. ~ 200 parts by mass, 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, a compound having an active hydrogen and a tertiary amino group in the same molecule. ~ 24 parts by mass.

The urethane-based polymer dispersant is produced according to a known method for producing a polyurethane resin. The solvent used for production is usually 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. Hydrocarbons such as, diacetone alcohol, isopropanol, second butanol, some alcohols such as tertiary butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl. An aprotonic polar solvent such as pyrrolidone or dimethylsulfoxide is used. These may be used alone or in combination of two or more.

In the above production, a urethanization reaction catalyst is usually used. Examples of this catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stanas octoate, iron-based catalysts such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. One type or two or more types such as a tertiary amine type can be mentioned.

<Measuring method of amine value>
The tertiary amine value of the dispersant is expressed by the amount of base per 1 g of solid content excluding the solvent in the dispersant sample and the equivalent mass of KOH, and can be measured by the following method.
Weigh 0.5 to 1.5 g of the dispersant sample in a 100 mL beaker and dissolve in 50 mL of acetic acid. using automatic titrator equipped with a pH electrode, to neutralization titration of this solution with HClO ₄ (perchloric acid) acetic acid solution of 0.1 mol / L. The amine value is calculated by the following equation with the inflection point of the titration pH curve as the titration end point.

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

When the isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time is improved.
The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. The weight average molecular weight (Mw) of the urethane-based polymer dispersant is particularly preferably 30,000 or less. When the weight average molecular weight (Mw) is at least the lower limit value, the dispersibility and dispersion stability tend to be good, and when the weight average molecular weight (Mw) is at least the upper limit value, the solubility is good and the dispersibility is also good. There is. When the molecular weight is 30,000 or less, the alkali developability tends to be good even when the pigment concentration is particularly high. Examples of such a particularly preferable commercially available urethane dispersant include DISPERBYK-167 and 182 (Big Chemie).

(E) The content of the dispersant is usually 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, based on the total solid content of the photosensitive resin composition. It is particularly preferably 10% by mass or less, usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more. The content ratio of the dispersant is usually 5 parts by mass or more, preferably 10 parts by mass or more, usually 200 parts by mass or less, and preferably 80 parts by mass or less with respect to 100 parts by mass of the coloring material (d). , 50 parts by mass or less is more preferable, 30 parts by mass or less is further preferable, and 20 parts by mass or less is particularly preferable. By setting the content ratio of the dispersant to be equal to or higher than the lower limit value, it tends to be easy to secure sufficient dispersibility, and by setting the content ratio to be lower than the upper limit value, the color density and sensitivity are not reduced without reducing the ratio of other components. , There is a tendency that the film forming property is sufficient.

In particular, as the dispersant, it is preferable to use a polymer dispersant and a pigment derivative (dispersion aid) in combination. In this case, the content ratio of the pigment derivative is the total solid content of the photosensitive resin composition of the present invention. On the other hand, it is usually 0.1% by mass or more, preferably 0.5% by mass or more, usually 10% by mass or less, preferably 5% by mass or less, and more preferably 2% by mass or less.

<Thiols>
The photosensitive resin composition of the present invention preferably contains thiols in order to increase the sensitivity and the adhesion to the substrate. Types of thiols include hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and trimethylolpropanetristhioglycolate. , Butanediol bisthiopropionate, trimethylolpropanetristhiopropionate, trimethylolpropanetristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, Ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate); (PGMB for short), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryl) Oxy) butane; (trade name; Karenz MT BD1, manufactured by Showa Denko Co., Ltd.), butanediol trimethylpropanetris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate); (trade name; Karenz) MT PE1, Showa Denko Co., Ltd.), Pentaerythritoltris (3-mercaptobutyrate), Ethylene glycol bis (3-mercaptoisobutyrate), Butanediol bis (3-mercaptoisobutyrate), Trimethylol propanetris (3-Mercaptoisobutyrate), trimethylolpropanetris (3-mercaptobutyrate); (TPMB for short), trimethylolpropanetris (2-mercaptoisobutyrate); (TPMIB for short), 1,3 5-Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion; (trade name; Karenz MT NR1, manufactured by Showa Denko Co., Ltd.) Etc., and various kinds of these can be used alone or in combination of two or more. Of these, polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1 are preferable, and among them, Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1 are more preferable, and Karenz MT PE1 is more preferable. Especially preferable.

When a thiol compound is used, the content ratio of the thiol compound is usually 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0, based on the total solid content of the photosensitive resin composition of the present invention. It is .5% by mass or more, usually 10% by mass or less, preferably 5% by mass or less. When the content ratio of the thiol compound is set to the lower limit value or more, the sensitivity decrease tends to be suppressed, and when the content ratio is set to the upper limit value or less, the storage stability tends to be improved.

<Solvent>
The photosensitive resin composition of the present invention usually contains (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, (d) a coloring material, and various materials used as necessary. Is used in a state of being dissolved or dispersed in an organic solvent.
As the organic solvent, it is preferable to select a solvent having a boiling point (pressure 1013.25 [hPa] condition; hereinafter, the same applies to all boiling points) in the range of 100 to 300 ° C. More preferably, it is a solvent having a boiling point of 120 to 280 ° C.
Examples of such an organic solvent 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-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol Glycol monoalkyl ethers such as monoethyl ether, tripropylene glycol methyl ether;

Glycoldialkyl 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 Glycolalkyl 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, diamil ether, ethylisobutyl ether, dihexyl ether;
Like 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, methylnonyl ketone, methoxymethylpentanone. 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;
Amilformate, ethylformate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methylisobutyrate, ethylene glycol acetate, ethylpropionate, propylpropionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Chain or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid;

Halogenated hydrocarbons such as butyl chloride, amilk chloride;
Etheretones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile.
Examples of commercially available solvents corresponding to the above include Mineral Spirit, Balsol # 2, Apco # 18 Solvent, Apco Thinner, and Sokal Solvent No. 1 and No. 2. Solvento # 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, Diglime (any of them). Product name) and so on.

These organic solvents may be used alone or in combination of two or more.
When forming the pixels of the color filter or the black matrix by the photolithography method, 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 to 230 ° C.
Of the above organic solvents, glycol alkyl ether acetates are preferable because they have a good balance of coatability, surface tension and the like, and the solubility of the constituent components in the composition is relatively high.

Further, the glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As other organic solvents that may be used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferable because of the solubility of the constituents in the composition. Glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate, and the viscosity of the photosensitive resin composition obtained later tends to increase, resulting in a decrease in storage stability. The proportion of glycol monoalkyl ethers 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, may be referred to as “high boiling point solvent”) in combination. By using such a high boiling point solvent in combination, the photosensitive resin composition becomes difficult to dry, but there is an 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 generation of foreign matter defects due to precipitation and solidification of coloring materials and the like at the tip of the slit nozzle. Among the various solvents mentioned above, 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 and 1,6-hexanediol diacetate are preferred.

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 particularly preferably 1% by mass to 30% by mass. By setting the content ratio of the high boiling point solvent to the above lower limit value or more, for example, it tends to be possible to prevent the coloring material and the like from precipitating and solidifying at the tip of the slit nozzle to cause foreign matter defects, and to set it to the above upper limit value or less. As a result, the drying temperature of the composition becomes slower, and problems such as poor tact in the vacuum drying process and pin marks of prebake tend to be avoided.

In the photosensitive resin composition of the present invention, the content ratio 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, further preferably 10% by mass or more, particularly preferably 12% 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. It is preferably 20% by mass or less.

<Other ingredients of the photosensitive resin composition>
In addition to the above-mentioned components, the photosensitive resin composition of the present invention may appropriately contain an adhesion improver, a coatability improver, a pigment derivative, a development improver, an ultraviolet absorber, an antioxidant and the like.

<Adhesion improver>
In order to improve the adhesion to the substrate, an adhesion improver may be contained, and examples thereof include a silane coupling agent and a titanium coupling agent, and a silane coupling agent is particularly preferable.
Examples of such a silane coupling agent include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X12-1050 (manufactured by Shin-Etsu Silicone Co., Ltd.), Z-. 6040, Z-6043, Z-6062 (manufactured by Toray Dow Corning Co., Ltd.) and the like can be mentioned. As the silane coupling agent, one type may be used, or two or more types may be used in combination in any combination and ratio.
Further, an adhesion improver other than the silane coupling agent may be contained in the photosensitive resin composition of the present invention, and examples thereof include a phosphoric acid-based adhesion improver and other adhesion improvers.

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

In the above general formulas (g1), (g2), and (g3), R ⁵¹ independently represents a hydrogen atom or a methyl group, l and l'are independently integers of 1 to 10, and m is independently 1 each. 2 or 3.
Examples of other adhesion improvers include TEGO ^* Add Bond LTH (manufactured by Evonik). These phosphoric acid group-containing compounds and other adhesives may be used alone or in combination of two or more.

The content ratio of the adhesion improver in the photosensitive resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and 0. 5% by mass or more is more preferable, 1% by mass or more is particularly preferable, 25% by mass or less is preferable, 20% by mass or less is more preferable, and 10% by mass or less is further preferable. It is particularly preferably 8% by mass or less, and most preferably 6% by mass or less. When it is set to the lower limit value or more, the adhesion to the substrate tends to be good, and when it is set to the upper limit value or less, the residue during alkaline development tends to be suppressed.

<Applicability improver>
The photosensitive resin composition of the present invention may contain a surfactant as a coatability improver in order to improve the coatability. As the surfactant, for example, various kinds such as anionic type, cationic type, nonionic type and amphoteric surfactant can be used. Among them, it is preferable to use a nonionic surfactant because it is unlikely to adversely affect various properties, and among them, a fluorine-based or silicon-based surfactant is 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 Big Chemie), and KP340. (Manufactured by Shinetsu Silicone), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Toray Dow Corning), DS-401 (manufactured by Daikin) , L-77 (manufactured by Nippon Unicar), FC4430 (manufactured by 3M Japan) and the like. As the surfactant, one type may be used, or two or more types may be used in combination in any combination and ratio.
The content ratio of the surfactant in the photosensitive resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0. It is more preferably 10% by mass or more, more preferably 1.0% by mass or less, still more preferably 0.7% by mass or less, still more preferably 0.5% by mass or less. , 0.3% by mass or less is particularly preferable. When the content ratio of the surfactant is not less than the lower limit value, the resist coating uniformity tends to be improved, and when it is not more than the upper limit value, the resist sensitivity tends not to be lowered.

<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-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindoleinone-based, dioxazine-based, anthraquinone-based, indanthrone-based, perylene-based, perinone-based, diketopyrrolopyrrole-based, and dioxazine. Derivatives such as phthalocyanines can be mentioned, but phthalocyanine-based and quinophthalone-based derivatives are preferable.

As the substituent of the pigment derivative, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group and the like are directly on the pigment skeleton or an alkyl group, an aryl group or a complex. Examples thereof include those bonded via a ring group or the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted into one pigment skeleton. Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivative, quinophthalone sulfonic acid derivative, anthraquinone sulfonic acid derivative, quinacridone sulfonic acid derivative, diketopyrrolopyrrole sulfonic acid derivative, dioxazine sulfonic acid derivative and the like. These may be used alone or in combination of two or more.

<Manufacturing method of photosensitive resin composition>
The photosensitive resin composition of the present invention (hereinafter, may be referred to as "resist") is produced according to a conventional method.
Usually, (d) the coloring material is preferably dispersed in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the (d) coloring material is made into fine particles by the dispersion treatment, the coating characteristics of the resist are improved. Further, (d) when a black color material is used as the color material, it contributes to the improvement of the light-shielding ability.

The dispersion treatment is usually preferably carried out in a system in which (d) a coloring material, a solvent, and if necessary, (e) a dispersant and (a) a part or all of an alkali-soluble resin are used in combination. (Hereinafter, the mixture to be subjected to the dispersion treatment and the composition obtained by the treatment may be referred to as "ink" or "pigment dispersion liquid".) In particular, when a polymer dispersant is used as the dispersant, the mixture is obtained. It is preferable because the thickening of the ink and the resist over time is suppressed (excellent in dispersion stability).
When the liquid containing all the components to be blended in the photosensitive resin composition is subjected to the dispersion treatment, the highly reactive component may be denatured due to the heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.

When (d) the coloring material is dispersed by a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. The dispersion treatment conditions are such that the temperature is usually 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. The dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment apparatus, etc., and is appropriately adjusted. The guideline for dispersion is to control the gloss of the ink so that the 20-degree mirror gloss (JIS Z8741) of the resist is in the range of 100 to 200. When the glossiness of the resist is at least the above lower limit value, the dispersion treatment is sufficient, coarse pigment (coloring material) particles are less likely to remain, and the developability, adhesion, resolution, etc. tend to be sufficient. There is. Further, when the gloss value is not more than the upper limit value, it tends to be possible to avoid that the pigment is crushed and a large number of ultrafine particles are generated, and the dispersion stability is rather impaired.

Next, the ink obtained by the above dispersion treatment and the above other components contained in the resist are mixed to obtain a uniform solution. In the resist manufacturing process, fine dust is often mixed in the liquid, so it is desirable to filter the obtained resist with a filter or the like.

[Cursed product]
A cured product can be obtained by curing the photosensitive resin composition of the present invention. The 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 or a colored spacer.

[Black Matrix]
Next, the black matrix using the photosensitive resin composition of the present invention will be described according to the production method thereof.

(1) Support The material of the support for forming the black matrix is not particularly limited as long as it has an appropriate strength. A transparent substrate is mainly used, and as the material, for example, polyester resin such as polyethylene terephthalate, polyolefin resin such as polypropylene and polyethylene, thermoplastic resin sheet such as polycarbonate, polymethylmethacrylate and polysulphon, and epoxy resin. , A heat-curable resin sheet such as an unsaturated polyester resin or a poly (meth) acrylic resin, or various types of glass. Among these, glass and heat-resistant resin are preferable from the viewpoint of heat resistance. Further, a transparent electrode such as ITO or IZO may be formed on the surface of the substrate. Other than the transparent substrate, it can be formed on the TFT array.

For the support, in order to improve the surface physical properties such as adhesiveness, if necessary, corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc. May be done.
The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. When the thin film forming treatment of various resins is performed, 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 with the above-mentioned photosensitive resin composition of the present invention, the photosensitive resin composition of the present invention is applied onto a transparent substrate, dried, and then coated. A photomask is placed on the surface, and a black matrix is formed by image exposure, development, and heat curing or photocuring as required through the photomask.

(3) Formation of Black Matrix (3-1) Application of Photosensitive Resin Composition The application of the photosensitive resin composition for black matrix on a transparent substrate is performed by a spinner method, a wire bar method, a flow coat method, or a die coat method. , The roll coating method, the spray coating method, or the like. Above all, according to the die coating method, the amount of the coating liquid used is significantly reduced, and there is no influence of mist or the like adhering when the spin coating method is used, and the generation of foreign substances is suppressed. It is preferable from.

The thickness of the coating film is usually preferably in the range of 0.2 to 10 μm after drying, more preferably in the range of 0.5 to 6 μm, and further preferably in the range of 1 to 4 μm. be. By setting the value to the upper limit or less, pattern development tends to be easy, and gap adjustment in the liquid crystal cell formation step tends to be easy. Further, when the value is equal to or higher than the lower limit, the desired color expression tends to be facilitated.

(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 according to the type of the solvent component, the performance of the dryer 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, and the like. It is selected in the range of 30 seconds to 3 minutes.

The higher the drying temperature, the better the adhesiveness of the coating film to the transparent substrate, but if it is too high, the alkali-soluble resin may be decomposed, inducing thermal polymerization and causing development failure. The step of drying the coating film may be a vacuum drying method in which the coating film is dried in a reduced pressure chamber without raising the temperature.

(3-3) Exposure Image exposure is performed by superimposing a negative mask pattern on a coating film of a photosensitive resin composition and irradiating light having a wavelength from the ultraviolet region to the visible region through the mask pattern. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, 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 the light source include a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, and a carbon arc. An optical filter can also be used when irradiating light of a specific wavelength for use.

(3-4) Development The black matrix according to the present invention is an aqueous solution containing an organic solvent or a surfactant and an alkaline compound after image exposure of a coating film made of a photosensitive resin composition with the above-mentioned light source. An image can be formed and produced on a substrate by development using. The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and potassium phosphate. , Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, 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), organic alkaline such as choline. Examples include compounds. These alkaline compounds may be a mixture of two or more kinds.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples thereof include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates and sulfosuccinic acid ester salts, and amphoteric surfactants such as alkyl betaines and amino acids.

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

(3-5) Thermosetting Treatment The substrate after development is subjected to a thermosetting treatment or a photocuring treatment, preferably a thermosetting treatment. The thermosetting treatment conditions at this time are selected in the range of 100 to 280 ° C., preferably 150 to 250 ° C., and the time is selected in the range of 5 to 60 minutes.
The height of the black matrix formed as described above is usually 0.5 to 5 μm, preferably 0.8 to 4 μm.
Further, 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, particularly preferably 4.0 or more, and most preferably 4.2 or more. ..

[Formation of other color filter images]
A photosensitive resin composition containing one of red, green, and blue coloring materials is applied onto a transparent substrate provided with a black matrix by the same process as in (3-1) to (3-5) above, and dried. After that, a photomask is superposed on the coating film, and a pixel image is formed through the photomask by image exposure, development, and if necessary, heat curing or photocuring to prepare a colored layer. By performing this operation on each of the three color photosensitive resin compositions of red, green, and blue, a color filter image can be formed. These orders are not limited to the above.

[Colored spacer]
The photosensitive resin composition of the present invention can also be used as a resist for a colored spacer in addition to the black matrix. When the spacer is used for the TFT type LCD, the TFT may malfunction as a switching element due to the light incident on the TFT, and the colored spacer is used to prevent this. For example, Japanese Patent Application Laid-Open No. 8-234212 The publication describes that the spacer has a light-shielding property. The colored spacer can be formed by the same method as the above-mentioned black matrix except that a mask for the colored spacer is used.

(3-6) Formation of transparent electrode A color filter is used as a part of parts such as a color display and a liquid crystal display device by forming a transparent electrode such as ITO on an image as it is, but the surface is smooth. If necessary, a top coat layer such as polyamide or polyimide can be provided on the image in order to improve the properties and durability. Further, in some applications such as a plane alignment type drive system (IPS mode), a transparent electrode may not be formed.

[Image display device]
The image display device of the present invention has a cured product obtained by curing the photosensitive resin composition of the present invention. The image display device is not particularly limited as long as it is a device that displays an image or a moving image, and examples thereof include a liquid crystal display device and an organic EL display described later.

[Liquid crystal display device]
The liquid crystal display device of the present invention has a cured product such as the black matrix, color filter pixels, and colored spacers of the present invention described above, and is not particularly limited in terms of the formation order and position of the color pixels and the black matrix. No.

A liquid crystal display device usually forms an alignment film on a color filter, sprays a spacer on the alignment film, attaches the spacer to the facing substrate to form a liquid crystal cell, and injects liquid crystal 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 adopted for forming the alignment film, and the thickness of the alignment film is several tens of nm. After the alignment film is hardened by heat firing, it is surface-treated by irradiation with ultraviolet rays or treatment with a rubbing cloth to obtain a surface state in which the inclination of the liquid crystal can be adjusted.

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

The gap for bonding to the facing 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 facing substrate, the parts other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then depressurized in a vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the inside of the chamber leaks to inject the liquid crystal into the liquid crystal cell. .. The degree of decompression in the liquid crystal cell is usually 1 × 10 − ² to 1 × 10 ⁻⁷ Pa, but preferably 1 × 10 ^{− 3} to ^{1 × 10 − 6} Pa. Further, it is preferable to heat the liquid crystal cell at the time of depressurization, and the heating temperature is usually 30 to 100 ° C, more preferably 50 to 90 ° C. The heat retention during depressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal display. A liquid crystal display device (panel) is completed by sealing the liquid crystal cell into which the liquid crystal is injected by curing the UV curable resin and sealing the liquid crystal injection port.

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

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

When an organic EL display is manufactured using the color filter of the present invention, for example, as shown in FIG. 1, a pattern formed by a photosensitive resin composition (that is, pixels 20 and adjacent to each other) is first placed on a transparent support substrate 10. A color filter in which a resin black matrix (not shown) provided between the pixels 20 is formed is produced, and an organic illuminant 500 is formed on the color filter via an organic protective layer 30 and an inorganic oxide film 40. The organic EL element 100 can be manufactured by laminating the above. At least one of the pixel 20 and the resin black matrix was produced by using the photosensitive resin composition of the present invention. As a method of laminating the organic illuminant 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 a color filter, or a method of sequentially forming a cathode 55. Examples thereof include a method of bonding the organic light emitter 500 formed on another substrate onto the inorganic oxide film 40. Using the organic EL element 100 thus produced, for example, the method described in "Organic EL Display" (Ohmsha, August 20, 2004, Luminous, Shizushi Tokito, Chihaya Adachi, Hideyuki Murata), etc. , An organic EL display can be manufactured.

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.

Next, the present invention will be described in more detail with reference to synthetic examples, examples and comparative examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

<Preparation of carbon black ink>
A carbon black ink was prepared by blending a pigment, a dispersant, a dispersion aid (pigment derivative), and a solvent according to the following composition and method.
Specifically, first, the solid content of the pigment, the dispersant, and the dispersion aid and the solvent were prepared so as to have the following amount ratios.
-Pigment: RAVEN1060U (manufactured by Biller, carbon black); 52.00 parts by mass-Dispersant: DISPERBYK-167 (manufactured by Big Chemie, basic urethane dispersant); 7.30 parts by mass (solid content conversion)
-Dispersion aid (pigment derivative): S12000 (manufactured by Lubrizol, phthalocyanine pigment derivative having an acidic group); 1.03 parts by mass-Solvent: propylene glycol monomethyl ether acetate (PGMEA); 112.04 parts by mass

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

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

50 g of an epoxy compound (epoxy equivalent 264) having the above chemical structure, 13.65 g of acrylic acid, 60.5 g of 3-methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of paramethoxyphenol were added to 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 obtained epoxy acrylate solution, 0.76 parts by mass of trimethylolpropane (TMP), 3.3 parts by mass of biphenyltetracarboxylic acid dianhydride (BPDA), 3.5 parts by mass of tetrahydrophthalic acid anhydride (THPA). The mass part 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 react.
When the resin solution became transparent, it was diluted with 3-methoxybutyl acetate (MBA) to prepare a solid content of 50% by mass, had an acid value of 115 mgKOH / g, and had a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC. ) 2,600 alkali-soluble resin (1) was obtained.

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

7.3 g of epoxy compound (epoxy equivalent 240) with the above chemical structure, 2.2 g of acrylic acid, 6.4 g of propylene glycol monomethyl ether acetate, 0.18 g of tetraethylammonium chloride, and 0.007 g of p-methoxyphenol were added to a thermometer and agitator. The mixture was placed in a flask equipped with a cooling tube and reacted at 100 ° C. with stirring 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 obtained epoxy acrylate solution, 0.4 parts by mass of trimethylolpropane (TMP), 3.5 parts by mass of biphenyltetracarboxylic acid dianhydride (BPDA), 0.06 parts by mass of tetrahydrophthalic acid anhydride (THPA). 40 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) and 14 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were 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 react, and the solid content was 40% by mass. An alkali-soluble resin (2) having an acid value of 100 mgKOH / g and a weight average molecular weight (Mw) of 10,400 in terms of polystyrene measured by GPC was obtained.

<Photopolymerization initiator (1)>

The photopolymerization initiator (1) having the above chemical structure synthesized by the method described in International Publication No. 2015/036910 was used. The obtained photopolymerization initiator (1) is dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a 0.01 mass% solution, which is absorbed using a spectrophotometer U-3900H (manufactured by Hitachi High-Tech Science). When the spectrum was measured, the maximum absorption wavelength in the wavelength range of 320 nm to 400 nm was 331 nm.

<Photopolymerization initiator (2)>

A photopolymerization initiator (2) having the above chemical structure synthesized by the method described in International Publication No. 2008/07786 was used. When the absorption spectrum was measured by the same method as that of the photopolymerization initiator (1), the maximum absorption wavelength was 368 nm.

<Photopolymerization initiator (3)>
As the photopolymerization initiator (3), TR-PBG-314 (compound having the following chemical structure) manufactured by Changzhou Strong Electronics New Materials Co., Ltd. was used.

When the absorption spectrum was measured by the same method as that of the photopolymerization initiator (1), the maximum absorption wavelength was 339 nm.

<Photopolymerization initiator (4)>
As the photopolymerization initiator (4), TR-PBG-358 (compound having the following chemical structure) manufactured by Changzhou Strong Electronics New Materials Co., Ltd. was used.

When the absorption spectrum was measured by the same method as that of the photopolymerization initiator (1), the maximum absorption wavelength was 344 nm.

<Photopolymerizable monomer>
Light acrylate PE-4A manufactured by Kyoeisha Chemical Co., Ltd. and KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd. were prepared as photopolymerizable monomers.

<Adhesion improver>
As the adhesion improver, KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd., which is a silane coupling agent, and KAYAMER PM-21 manufactured by Nippon Kayaku Co., Ltd., which is a phosphoric acid-based adhesion improver, were prepared.

<Applicability improver>
As a coatability improver, Megafuck F-554 (fluorine-containing group / lipophilic group-containing oligomer, nonionic type surfactant) manufactured by DIC Co., Ltd., which is a surfactant, was prepared.

<Example 1>
(Preparation of black resist 1)
Using the carbon black ink prepared in <Preparation of carbon black ink>, each component was added so as to have the ratio shown in Table 1, and the mixture was stirred and dissolved by a stirrer to prepare black resist 1. The total solid content in the black resist 1 is 15% by mass.

The meanings of the abbreviations for the solvents in Table 1 are as follows.
PGMEA: Propylene Glycol Monomethyl Ether Acetate MBA: 3-Methoxybutyl Acetate EDGAC: Diethylene Glycol Monoethyl Ether Acetate

<Example 2>
(Preparation of black resist 2)
In the black resist 1 shown in Table 1, the total amount of the photopolymerization initiators remains the same, except that the mixing ratio (% by mass) of the photopolymerization initiators (1) and (2) is changed as shown in Table 2. , Black resist 2 having a solid content concentration of 15% by mass was prepared by the same method as that of black resist 1.

<Example 3>
(Preparation of black resist 3)
In the black resist 1 shown in Table 1, the total amount of the photopolymerization initiators remains the same, except that the mixing ratio (% by mass) of the photopolymerization initiators (1) and (2) is changed as shown in Table 2. , Black resist 3 having a solid content concentration of 15% by mass was prepared by the same method as that of black resist 1.

<Comparative Example 1>
(Preparation of black resist 4)
In the black resist 1 shown in Table 1, the total amount of the photopolymerization initiators remains the same, except that the mixing ratio (% by mass) of the photopolymerization initiators (1) and (2) is changed as shown in Table 2. , Black resist 4 having a solid content concentration of 15% by mass was prepared by the same method as that of black resist 1.

<Comparative Example 2>
(Preparation of black resist 5)
In the black resist 1 shown in Table 1, the total amount of the photopolymerization initiators remains the same, except that the mixing ratio (% by mass) of the photopolymerization initiators (1) and (2) is changed as shown in Table 2. , Black resist 5 having a solid content concentration of 15% by mass was prepared by the same method as that of black resist 1.

<Example 4>
(Preparation of black resist 6)
In the black resist 2 of Example 2, the total amount of the photopolymerization initiator remains the same, and the photopolymerization initiator (2) is changed to the photopolymerization initiator (3). A black resist 6 having a component concentration of 15% by mass was prepared.

<Example 5>
(Preparation of black resist 7)
In the black resist 2 of Example 2, the total amount of the photopolymerization initiator remains the same, and the photopolymerization initiator (2) is changed to the photopolymerization initiator (4). A black resist 7 having a component concentration of 15% by mass was prepared.

(Evaluation of black resist)
(1) Preparation of Black Matrix (BM) Fine Line Pattern The prepared black resists 1 to 7 were applied to a glass substrate with a spin coater, dried under reduced pressure, and then dried on a hot plate at 90 ° C. for 100 seconds. The coating conditions were adjusted so that the coating film thickness was about 1.2 μm. Subsequently, the obtained dry coating film was subjected to a high-pressure mercury lamp (ADH-3000M-F-N manufactured by ORC Manufacturing Co., Ltd., without an optical filter) using an exposure machine (EXF-2829-F-00 manufactured by ORC Manufacturing Co., Ltd.). At 35 mJ / cm ² , pattern exposure (proximity gap: 180 μm) was performed through an exposure mask having an opening width of 1 to 10 μm (in 1 μm increments) and a linear opening of 15 μm. Then, at room temperature (23 ° C.), a KOH aqueous solution prepared to 0.04% by mass with ultrapure water was used as an alkaline developing solution for 2.2 times the dissolution time, and spray development (spray pressure: 0.1 MPa). Then, after removing the unexposed portion, spray cleaning (spray pressure: 0.1 MPa) was performed with ultrapure water to form a BM fine line pattern. The dissolution time was the time until the black resist film in the unexposed portion was dissolved and the surface of the substrate was visible during the development process, and the dissolution time of each black resist was in the range of 20 to 30 seconds.

(2) Evaluation of BM fine line pattern The BM fine line pattern produced after development was observed with an optical microscope to confirm the BM fine line formation state, and the fine line adhesion and sensitivity were evaluated. The results are shown in Table 3. The fine line adhesion and sensitivity were evaluated according to the following criteria.

(Thin line adhesion evaluation)
In the BM fine wire, the adhesive surface of the BM fine wire / glass substrate may be eroded during alkaline development to cause insertion, resulting in poor wire adhesion. A line pattern portion of 10 μm or less was observed with an optical microscope. For example, when a pattern of 8 μm or more adhered and a pattern of 7 μm or less was peeled off, the fine line adhesion was evaluated as 8 μm and classified as follows (here). Then, for example, a pattern corresponding to the width of the opening of the exposure mask of 7 μm is described as a pattern of 7 μm). If the evaluation is "○", the fine line adhesion is good, if it is "◎", it can be evaluated to be even better, and if it is "×", the fine line adhesion is evaluated to be poor.
⊚: Fine lines having a pattern of 7 μm or more are in close contact with each other.
〇: Fine lines of patterns of 8 μm or more are in close contact (patterns of 7 μm or less are peeled off).
X: Fine lines of patterns of 9 μm or more are in close contact (patterns of 8 μm or less are peeled off).

(Sensitivity evaluation)
As the exposure sensitivity of the black resist as a photosensitive resin composition increases, the line width of the BM fine lines formed tends to increase. The line width of the line pattern of 15 μm was measured with an optical microscope, and the determination of sensitivity was classified as follows (for example, the pattern corresponding to the width of the opening of the exposure mask of 15 μm is described as a pattern of 15 μm. is doing.). If the evaluation is "◯", it can be evaluated that the sensitivity is good, and if the evaluation is "x", it is evaluated that the sensitivity is low.
◯: The line width of the 15 μm pattern is 15 μm or more.
X: The line width of the 15 μm pattern is less than 15 μm.

As shown in Table 3, all of the BM fine wires of Examples 1 to 5 had good thin line adhesion and sensitivity. The BM fine wire of Comparative Example 1 showed high sensitivity, but the result was that the fine wire adhesion was low. Further, the BM fine wire of Comparative Example 2 showed good adhesion to the fine wire, but the sensitivity was low.

In Comparative Example 1, the surface of the BM is strongly cured, but the inside of the BM is not sufficiently cured. Therefore, it is considered that the fine line adhesion is poor even though the line width is wide. In Comparative Example 2, the surface of the BM is loosely cured, but the inside of the BM is strongly cured, so that it is considered that the fine line adhesion is good even though the line width is narrow. Further, in Examples 1 to 5, it is considered that the well-balanced progress of hardening of the BM surface and the inside leads to both fine line adhesion and high sensitivity.

In Examples 1 to 5, the line width becomes thick due to the high sensitivity, but it is desirable because there are many merits from the following viewpoints.
・ The amount of photopolymerization initiator can be reduced as much as there is a margin in sensitivity, and by replacing the reduced amount with an alkali-soluble resin or photopolymerizable monomer, it can be allocated to improve performance such as development resistance and substrate adhesion. ..
-As the amount of exposure required to form the target line width decreases, the exposure speed can be increased and productivity is improved. On the other hand, Comparative Example 1 is also a result of high sensitivity, but since the curing inside the BM is insufficient, if the amount of the photopolymerization initiator is reduced or the exposure amount is reduced, further deterioration of fine line adhesion is caused.

Although the detailed mechanism for the effect of the present invention has not been clarified, it is considered as follows. That is, the phenyl sulfide-based photopolymerization initiator has an excellent UV absorption capacity near 330 nm, but the benzofuran portion of the condensed heterocycle possessed by the photopolymerization initiator (c1) represented by the general formula (I) is a coloring material. In particular, by enhancing the interacting force with carbon black, the adsorption of the photopolymerization initiator (c1) on the surface of the coloring material particles is promoted. The light absorbed by the coloring material does not contribute to the polymerization and is a major cause of the decrease in exposure sensitivity. However, when the photopolymerization initiator covers the surface of the coloring material, the light absorption rate for the photopolymerization initiator is improved. Further, the adsorption of the photopolymerization initiator on the coloring material relatively lowers the concentration of the photopolymerization initiator in the resin component, so that the light transmission to the deep part is improved. It is considered that this improves the internal curability of the resist film and leads to the improvement of the fine line adhesion.

However, since the photopolymerization initiator (c1) alone uses only a part of the low wavelength side of the UV wavelength range of the exposure light source and sufficient sensitivity cannot be obtained, the maximum absorption wavelength is in the long wavelength range. Sensitivity, especially surface sensitivity, can be raised by combining with the photopolymerization initiator (c2). Since there is a difference in the maximum absorption wavelength between the photopolymerization initiator (c1) and the photopolymerization initiator (c2), the influence on the internal curability due to the combined use can be suppressed. It is considered that these made it possible to increase the surface sensitivity and the internal curing at the same time.
From the above, it can be seen that by using the photosensitive resin composition of the present invention, it is possible to provide a photosensitive resin composition having high sensitivity and excellent fine wire adhesion performance.

Although the present invention has been described in detail with particular embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible without departing from the intent and scope of the invention. This application is based on a Japanese patent application filed on September 16, 2016 (Japanese Patent Application No. 2016-181932), which is incorporated by reference in its entirety.

10 Transparent support substrate 20 pixels 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode 51 Hole injection layer 52 Hole transport layer 53 Light emitting layer 54 Electron injection layer 55 Cathode 100 Organic EL element 500 Organic light emitter

Claims (10)

A photosensitive resin composition containing (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, and (d) a coloring material.
The (c) photopolymerization initiator is a photopolymerization initiator (c1) represented by the following general formula (I), and a photopolymerization initiator having a maximum absorption wavelength of 334 nm or more in the wavelength range of 320 nm to 400 nm. It contains c2) (however, the combination of the photopolymerization initiator (c1) and 2,4-diethylthioxanthone, and the photopolymerization initiator (c1) and bis (2,4,6-trimethylbenzoyl)-. Excluding the combination with phenylphosphin oxide.) ,
A photosensitive resin composition, wherein the content ratio of the photopolymerization initiator (c1) in the (c) photopolymerization initiator is 30% by mass or more and 60% by mass or less.

(In formula (I), R ¹ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ² represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
k represents 0 or 1.
R ^{3 to} R ⁶ each independently represent an arbitrary monovalent substituent.
l, m and o each independently represent an integer of 0 to 3. n represents 0 or 1. ) The photosensitive resin composition according to claim 1, wherein the content ratio of the (c) photopolymerization initiator with respect to the total solid content is 2% by mass or more. The photosensitive resin composition according to claim 1 or 2, wherein the content ratio of the photopolymerization initiator (c2) in the (c) photopolymerization initiator is 40% by mass or more. The photosensitive resin composition according to any one of claims 1 to 3, wherein the photopolymerization initiator (c2) is a photopolymerization initiator having a fluorene skeleton or a carbazole skeleton. The photosensitive resin composition according to claim 4, wherein the photopolymerization initiator (c2) is a photopolymerization initiator represented by the following general formula (II).

(In formula (II), R ⁷ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ⁸ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
p represents 0 or 1.
R ⁹ represents any monovalent substituent. q represents an integer of 0 to 3.
X represents −N (R ¹⁰ ) − or −C (R ¹¹ ) (R ¹² ) −.
R ^{10 to} R ¹² each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R ¹¹ and R ¹² may be coupled to each other to form a ring. ) The photosensitive resin composition according to any one of claims 1 to 5, wherein the coloring material (d) is carbon black. The photosensitive resin composition according to any one of claims 1 to 6, wherein the content ratio of the coloring material (d) with respect to the total solid content is 30% by mass or more. The photosensitive resin composition according to any one of claims 1 to 7, wherein the alkali-soluble resin (a) contains an epoxy (meth) acrylate resin having a carboxyl group. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 8. An image display device having the cured product according to claim 9.

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