CN109791357B

CN109791357B - Photosensitive resin composition, cured product and image display device

Info

Publication number: CN109791357B
Application number: CN201780056225.0A
Authority: CN
Inventors: 植松卓也; 关口直人
Original assignee: Mitsubishi Chemical Corp
Current assignee: Mitsubishi Chemical Corp
Priority date: 2016-09-16
Filing date: 2017-09-13
Publication date: 2023-01-10
Anticipated expiration: 2037-09-13
Also published as: WO2018052024A1; KR20190051976A; TWI745431B; JP7283519B2; JPWO2018052024A1; TW201818152A; CN109791357A; JP2018156093A; JP6341351B1; KR102402726B1; JP6977662B2; JP2022028782A

Abstract

The invention provides a photosensitive resin composition with high sensitivity and excellent fine line adhesion. The photosensitive resin composition comprises (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, and (d) a coloring material, wherein the photopolymerization initiator (c) comprises a photopolymerization initiator (c 1) represented by the general formula (I) and a photopolymerization initiator (c 2) having a maximum absorption wavelength of 334nm or more in a wavelength range of 320nm to 400 nm. (in the formula (I), R ¹ ～R ⁶ K, l, m, n and o are the same as defined in the specification. )

Description

Photosensitive resin composition, cured product and image display device

Technical Field

The 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 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 (BM) capable of forming a fine line with high sensitivity and high definition.

Background

The color filter is generally formed by forming a black matrix on the surface of a transparent substrate such as glass or plastic, and then sequentially forming 3 or more different color pixels such as red, green, and blue in a pattern such as a lattice pattern, a stripe pattern, or a mosaic pattern. The pattern size varies depending on the application of the color filter and the color of each color, but is usually about 5 to 700 μm.

As a representative manufacturing method of a color filter, a pigment dispersion method is known. In the case of manufacturing a color filter by the pigment dispersion method, first, a photosensitive resin composition containing a black pigment is applied on a transparent substrate and then dried, and further, after image exposure and development, the BM is formed by curing by a high-temperature treatment at 200 ℃. By repeating this operation for each color of red, green, blue, or the like, a color filter is formed.

The BMs are usually arranged in a lattice, stripe, or mosaic form between pixels of red, green, blue, etc., and have the effect of improving contrast or preventing light leakage by suppressing color mixing between pixels. Therefore, the BM is required to have high light-shielding properties. Further, since the edge portions of the pixels such as red, green, and blue pixels formed after the formation of the BM partially overlap with the BM, a level difference is formed in the overlapping portion due to the film thickness of the BM. In the overlapped portion, flatness of the pixel is impaired, and non-uniformity of the liquid crystal cell gap or disorder of the liquid crystal alignment occurs, which causes a reduction in display capability. Therefore, in recent years, it has been desired to make the film thickness of BM thin, and in order to exhibit sufficient light-shielding properties even when the film thickness is made thin, the content ratio of the pigment in the photosensitive resin composition is increased. For this reason, the proportion of the photopolymerization initiator that can be added tends to decrease, and a highly sensitive initiator that can maintain the degree of crosslinking even if added in a small amount is required.

On the other hand, in order to achieve energy saving and a long life of a mobile phone battery, it is a development to reduce the output of a backlight, and in order to realize image display with high luminance even under such a condition, thinning of BM as a light shielding portion is advanced. In recent years, in the market of liquid crystal displays, miniaturization of tablet personal computers and the like has become mainstream, and in large-sized televisions, demands for high resolution have been increasing. For these reasons, the expectation for high BM thinning is increasing, and in recent years, the line width of thin BM lines has been increasing from about 10 μm, which is conventionally used, to about 6 to 8 μm, which is currently required. If the pattern line width of the exposure mask enters a range smaller than 10 μm, the influence by diffraction of transmitted light becomes large, and the large portion causes a decrease in the amount of light reaching the BM surface. For this reason, highly sensitive initiators are required. In the development after exposure, the development time is usually set long in order to remove the residue, but this causes dissolution (embedment) of the BM/substrate interface to proceed, and peeling of the line pattern is likely to occur. When the pattern line width is 10 μm or more, the thin line adhesion can be maintained even if the insertion of about 1 to 2 μm (about 2 to 4 μm in total on both sides of the line) occurs, but in the thin line pattern of less than 10 μm, the adhesion area of BM/substrate becomes small, and the reduction range of the development adhesion per 1 μm narrowing of the line width becomes significantly large. In particular, in the shower development method used in a color filter manufacturing apparatus and the like, since the physical adhesion of BM is also required, it is difficult to form a fine line pattern of less than 10 μm. Therefore, it is necessary to improve the adhesion of the thin line by means of improving internal curability during exposure.

In view of such background, there is a demand for photosensitive resin compositions for BM which have high sensitivity and excellent adhesion to thin lines of less than 10 μm.

Patent document 1 describes the following: the oxime ester compound having a carbazolyl structure, which has been nitrated, is a highly sensitive photopolymerization initiator that can efficiently absorb light having a long wavelength of 405nm or 365nm to be activated. Patent document 2 describes the following: oxime ester compounds with benzo-unsaturated 5-membered ring-carbonyls are highly sensitive.

Documents of the prior art

Patent literature

Patent document 1: international publication No. 2008/078678

Patent document 2: international publication No. 2015/036910

Disclosure of Invention

Problems to be solved by the invention

The present inventors have found that when BM evaluation is performed using the photopolymerization initiator described in patent document 1, the sensitivity is improved, but the fine line adhesion in the shower development method is insufficient. In addition, when BM evaluation is performed using the photopolymerization initiator described in patent document 2, fine line adhesion is good, but the line width is narrowed, the film weight at the top of the pattern is reduced, and the sensitivity is insufficient.

Accordingly, an object of the present invention is to provide a photosensitive resin composition having high sensitivity and excellent adhesion to a thin line.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by incorporating a specific combination of photopolymerization initiators into a photosensitive resin composition. That is, the gist of the present invention is as follows.

[1] A photosensitive resin composition comprising (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, and (d) a coloring material,

wherein the photopolymerization initiator (c) contains a photopolymerization initiator (c 1) represented by the following general formula (I) and a photopolymerization initiator (c 2) having a maximum absorption wavelength of 334nm or more in a wavelength range of 320nm to 400 nm.

[ chemical formula 1]

(in the formula (I), R ¹ Represents an alkyl group optionally having a substituent or an aromatic ring group optionally having a substituent;

R ² represents an alkyl group optionally having a substituent or an aromatic ring group optionally having a substituent;

k represents 0 or 1;

R ³ ～R ⁶ each independently represents an arbitrary substituent having a valence of 1;

l, m and o each independently represent an integer of 0 to 3, and n represents 0 or 1. )

[2] The photosensitive resin composition according to the above [1], wherein a 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 of the photopolymerization initiator (c 1) in the photopolymerization initiator (c) is 1% by mass or more.

[4] The photosensitive resin composition according to any one of the above [1] to [3], wherein the photopolymerization initiator (c 2) is a photopolymerization initiator having a fluorene skeleton or a carbazole skeleton.

[5] The photosensitive resin composition according to the above [4], wherein the photopolymerization initiator (c 2) is a photopolymerization initiator represented by the following general formula (II).

[ chemical formula 2]

(in the formula (II), R ⁷ Represents an alkyl group optionally having a substituent or an aromatic ring group optionally having a substituent;

R ⁸ represents an alkyl group optionally having a substituent or an aromatic ring group optionally having a substituent;

p represents 0 or 1;

R ⁹ represents an optional substituent having a valence of 1; q represents an integer of 0 to 3;

x represents-N (R) ¹⁰ ) -or-C (R) ¹¹ )(R ¹² )-；

R ¹⁰ ～R ¹² Each independently represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aromatic ring group, R ¹¹ And R ¹² The ring may be bonded to each other to form a ring. )

[6] The photosensitive resin composition according to any one of the above [1] to [5], wherein the coloring material (d) is carbon black.

[7] The photosensitive resin composition according to any one of the above [1] to [6], wherein a content ratio of the color material (d) to the total solid content is 30% by mass or more.

[8] The photosensitive resin composition according to any one of the above [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 the above [1] to [8 ].

[10] An image display device comprising the cured product according to [9 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a photosensitive resin composition having high sensitivity and excellent adhesion to a thin line can be provided.

Drawings

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

Description of the symbols

10. Transparent support substrate

20. Pixel

30. Organic protective layer

40. Inorganic oxide film

50. Transparent anode

51. Hole injection layer

52. Hole transport layer

53. Luminescent layer

54. Electron injection layer

55. Cathode electrode

100. Organic EL element

500. Organic light-emitting body

Detailed Description

The present invention is not limited to the following embodiments, and can be carried out with various modifications within the scope of the gist thereof.

In the present invention, the "(meth) acrylic acid" means "acrylic acid and/or methacrylic acid", and the same applies to the "(meth) acrylate" and the "(meth) acryloyl group".

In the present invention, all percentages and parts by mass are the same as percentages and parts by weight.

In the present invention, the "total solid content" refers to all components other than the solvent contained in the photosensitive resin composition or the ink described later.

In the present invention, the weight average molecular weight refers to a weight average molecular weight (Mw) in terms of polystyrene obtained by GPC (gel permeation chromatography).

In the present invention, unless otherwise specified, the "amine number" represents an amine number in terms of an effective solid content, and is a value represented by the weight of KOH equivalent to the amount of base per 1g of solid content of the dispersant. The measurement method is as described below.

[ 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, wherein the photopolymerization initiator (c) contains a photopolymerization initiator (c 1) represented by the following general formula (I) and a photopolymerization initiator (c 2) having a maximum absorption wavelength of 334nm or more in a wavelength range of 320nm to 400 nm. In the present invention, the "maximum absorption wavelength" of the photopolymerization initiator (c) means a maximum absorption wavelength in a wavelength range of 320nm to 400 nm.

[ chemical formula 3]

In the formula (I), R ¹ Represents an alkyl group optionally having a substituent or an aromatic ring group optionally having a substituent;

k represents 0 or 1;

l, m and o each independently represent an integer of 0 to 3, and n represents 0 or 1.

The photosensitive resin composition of the present invention may further contain a dispersant and thiols, and may further contain other compounding ingredients such as an adhesion improving agent, a coatability improving agent, a development improving agent, an ultraviolet absorber, an antioxidant, and a pigment derivative as necessary, and each compounding ingredient is usually used in a state of being dissolved or dispersed in an organic solvent.

The invention is characterized in that: in the photosensitive resin composition, (c) the photopolymerization initiator contains a photopolymerization initiator (c 1) and a photopolymerization initiator (c 2). First, the photopolymerization initiator (c) will be described.

[ c ] photopolymerization initiator

The photopolymerization initiator (c) in the present invention contains a photopolymerization initiator (c 1) represented by the general formula (I) described later and a photopolymerization initiator (c 2) having a maximum absorption wavelength of 334nm or more.

< photopolymerization initiator (c 1) >

The photopolymerization initiator (c 1) is a photopolymerization initiator represented by the following general formula (I).

[ chemical formula 4]

k represents 0 or 1;

As described above, it is considered that the inclusion of the photopolymerization initiator (c 1) represented by the general formula (I) promotes the adsorption of the photopolymerization initiator to the surface of the color material particles, improves the light absorption rate of the photopolymerization initiator at the time of exposure, improves the UV (Ultraviolet) light transmittance of the resin component, improves the internal curability, and improves the adhesion to thin lines.

(R ¹ )

In the above formula (I), R ¹ Represents an alkyl group optionally having a substituent or an aromatic ring group optionally having a substituent.

R ¹ The alkyl group in (2) may be linear, branched or cyclic, or a combination thereof. The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, and is preferably 12 or less, more preferably 6 or less, further preferably 3 or less, and particularly preferably 2 or less. When the number of carbon atoms of the alkyl group is not more than the above upper limit, the crosslinking density tends to be increased.

Specific examples of the alkyl group include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl and the like. Among these alkyl groups, 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 even more preferable.

Examples of the substituent optionally contained in the alkyl group 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 or I, a hydroxyl group, a nitro group, etc., and a methoxy group or a hydroxyl group is preferable from the viewpoint of solvent solubility. From the viewpoint of sensitivity, the compound is preferably unsubstituted.

As R ¹ As the aromatic ring group in (3), an aromatic ring group and an aromatic heterocyclic group are exemplified. The number of carbon atoms is usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and still more preferably 8 or less. When the number of carbon atoms in the aromatic ring group is not less than the lower limit, the storage stability tends to be good, and when the number is not more than the upper limit, the solvent solubility tends to be good.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring with 1 free valence perylene ring, tetracene ring, pyrene ring, benzopyrene ring,

A ring, a benzophenanthrene ring, an acenaphthene ring, an anthryl ring, a fluorene ring, etc.

The aromatic heterocyclic group 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, having 1 free valence benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring,

A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring

An azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, and triazine ring,

A pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, etc.

Of these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having 1 free valence is preferable, and a benzene ring having 1 free valence is more preferable.

Examples of the optional substituent of the aromatic ring group 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, a halogen atom such as F, cl, br or I, a hydroxyl group, a nitro group and the like, and a methoxy group or a hydroxyl group is preferable from the viewpoint of solubility in a solvent. From the viewpoint of sensitivity, the compound is preferably unsubstituted.

Among these, R is R from the viewpoint of curability ¹ Preferably an alkyl group optionally having a substituent, more preferably an unsubstituted alkyl groupOne step is preferably methyl.

(R ² )

In the above formula (I), R ² Represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.

R ² The alkyl group in (b) may be linear, branched or cyclic, or a combination thereof, and is preferably linear or branched, more preferably branched, from the viewpoint of solvent solubility.

The number of carbon atoms of the alkyl group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, further preferably 4 or more, particularly preferably 5 or more, and preferably 10 or less, more preferably 8 or less, further preferably 7 or less, and particularly preferably 6 or less. When the number of carbon atoms of the alkyl group is not less than the lower limit, the solvent solubility tends to be good, and when the number of carbon atoms is not more than the upper limit, the sensitivity tends to be high.

Specific examples of the alkyl group include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl and the like. Among these alkyl groups, 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.

Examples of the substituent optionally contained in the alkyl group 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, a halogen atom such as F, cl, br or I, a hydroxyl group and the like, and an alkoxy group having 1 to 3 carbon atoms is preferable from the viewpoint of solvent solubility. From the viewpoint of sensitivity, the compound is preferably unsubstituted.

As R ² As the aromatic ring group in (3), an aromatic ring group and an aromatic heterocyclic group are exemplified. The number of carbon atoms is usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and still more preferably 8 or less. When the number of carbon atoms in the aromatic ring group is not less than the lower limit, the molecule tends to be stable, andin addition, when the content is not more than the above upper limit, the solubility in a solvent tends to be good.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, perylene derivative having 1 free valence,

The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, imidazole, or imidazole ring having 1 free valence,

Examples of the substituent optionally contained in the aromatic ring group 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, a halogen atom such as F, cl, br or I, a hydroxyl group, a nitro group and the like, and an alkoxy group or a hydroxyl group having 1 to 3 carbon atoms is preferable from the viewpoint of solubility in a solvent. From the viewpoint of sensitivity, the compound is preferably unsubstituted.

Among these, R is, from the viewpoint of sensitivity ² Preferably, the alkyl group is an optionally substituted alkyl group, more preferably an unsubstituted alkyl group, and still more preferably an isopentyl group.

(k)

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

(R ³ ～R ⁶ )

In the above formula (I), R ³ ～R ⁶ Each independently represents an arbitrary substituent having a valence of 1.

As the optional 1-valent substituent, there may be mentioned: an alkyl group having 1 to 10 carbon atoms such as a methyl group or an ethyl group; alkoxy groups having 1 to 10 carbon atoms such as methoxy group and ethoxy group; F. halogen atoms such as Cl, br, I, etc.; an acyl group having 1 to 10 carbon atoms; an alkyl ester group having 1 to 10 carbon atoms; an alkoxycarbonyl group having 1 to 10 carbon atoms; a halogenated alkyl group having 1 to 10 carbon atoms; an aromatic ring group having 4 to 10 carbon atoms; an amino group; an aminoalkyl group having 1 to 10 carbon atoms; a hydroxyl group; a nitro group; CN groups, and the like. Among these substituents, from the viewpoint of solvent solubility, methyl and methoxy groups are preferable, and methyl is more preferable.

At R ³ 、R ⁴ And R ⁶ Wherein when l, m and o are 2 or more, plural R' s ³ 、R ⁴ And R ⁶ Or 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 each preferably 0 or 1, and more preferably 0. In addition, from the viewpoint of sensitivity, n is preferably 0.

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

[ chemical formula 5]

In the formula (I-1), R ¹ ～R ⁶ And k to o are the same as in the above formula (I).

The maximum absorption wavelength of the photopolymerization initiator (c 1) is not particularly limited, but from the viewpoint of sensitivity, is preferably 322nm or more, more preferably 325nm or more, further preferably 328nm or more, still more preferably 329nm or more, particularly preferably 330nm or more, and preferably 337nm or less, more preferably 336nm or less, further preferably 334nm or less, still more preferably 333nm or less. Within the above range, light emitted from the UV light source between the 333nm bright line and the 365nm bright line (i line) tends to be effectively utilized.

The method for producing the photopolymerization initiator (c 1) is not particularly limited, and for example, the method described in international publication No. 2015/036910 can be used.

Specific examples of the photopolymerization initiator (c 1) include the following photopolymerization initiators.

[ chemical formula 6]

[ chemical formula 7]

[ chemical formula 8]

[ chemical formula 9]

The photopolymerization initiator (c) in the present invention contains a photopolymerization initiator (c 2) having a maximum absorption wavelength of 334nm or more in addition to the photopolymerization initiator (c 1).

< photopolymerization initiator (c 2) >

The photopolymerization initiator (c 2) has a maximum absorption wavelength of 334nm or more.

In this manner, it is considered that by using a photopolymerization initiator (c 2) having a maximum absorption wavelength of 334nm or more in addition to the photopolymerization initiator (c 1), the wavelength range of light that can be effectively utilized becomes wide, and the sensitivity becomes good.

The maximum absorption wavelength of the photopolymerization initiator (c 2) is not particularly limited as long as it is 334nm or more, but from the viewpoint of sensitivity, it is preferably 335nm or more, more preferably 336nm or more, further preferably 338nm or more, further preferably 340nm or more, particularly preferably 345nm or more, most preferably 350nm or more, and further preferably 390nm or less, more preferably 380nm or less, further preferably 375nm or less, particularly preferably 370nm or less. When the maximum absorption wavelength of the photopolymerization initiator (c 2) is not less than the lower limit, internal curing tends to be high, and when it is not more than the upper limit, high sensitivity tends to be achieved.

Further, the difference in the maximum absorption wavelength between the photopolymerization initiator (c 2) and the photopolymerization initiator (c 1) is preferably 5nm or more, more preferably 10nm or more, further preferably 20nm or more, particularly preferably 30nm or more, and further preferably 60nm or less, more preferably 50nm or less, further preferably 40nm or less, and a combination of the photopolymerization initiator (c 1) and the photopolymerization initiator (c 2) having an appropriate maximum absorption wavelength may be selected and used. When the difference between the maximum absorption wavelengths of the photopolymerization initiator (c 1) and the photopolymerization initiator (c 2) is equal to or greater than the lower limit, the wavelength range of light that can be effectively used tends to be wide and sensitivity tends to be high, and when the difference is equal to or less than the upper limit, sensitivity to i-line (365 nm) of UV light tends to be high.

The chemical structure of the photopolymerization initiator (c 2) is not particularly limited, and an oxime ester photopolymerization initiator is preferable from the viewpoint of sensitivity, and a photopolymerization initiator having a fluorene skeleton or a carbazole skeleton is particularly preferable. The term "having a fluorene skeleton or a carbazole skeleton" means that a fluorene ring or a carbazole ring is present in the molecular structure, and these rings may be substituted.

From the viewpoint of surface curability, the photopolymerization initiator (c 2) is preferably a photopolymerization initiator represented by the following general formula (II).

[ chemical formula 10]

In the formula (II), R ⁷ Represents an alkyl group optionally having a substituent or an aromatic ring group optionally having a substituent;

p represents 0 or 1;

R ⁹ represents an optional substituent having a valence of 1, and q represents an integer of 0 to 3;

x represents-N (R) ¹⁰ ) -or-C (R) ¹¹ )(R ¹² )-；

R ¹⁰ ～R ¹² Each independently represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aromatic ring group, R ¹¹ And R ¹² The ring may be bonded to each other to form a ring.

(R ⁷ )

In the above formula (II), R ⁷ Represents an alkyl group optionally having a substituent or an aromatic ring group optionally having a substituent.

R ⁷ The alkyl group in (1) may be linear or branchedThe polymer may be a cyclic one or a combination of these. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 10 or less, more preferably 7 or less, further preferably 5 or less, particularly preferably 3 or less, most preferably 2 or less, and usually 1 or more. When the number of carbon atoms of the alkyl group is not more than the above upper limit, the crosslinking density tends to be increased.

Examples of the substituent optionally contained in the alkyl group 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, a halogen atom such as F, cl, br or I, a hydroxyl group, etc., and an alkoxy group having 1 to 3 carbon atoms is preferable from the viewpoint of solvent solubility. From the viewpoint of sensitivity, the compound is preferably unsubstituted.

As R ⁷ The aromatic ring group in (1) includes an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and still more preferably 8 or less. When the number of carbon atoms of the aromatic ring group is not less than the lower limit, the molecule tends to be stable, and when the number is not more than the upper limit, the solubility in a solvent tends to be good.

A ring, a benzophenanthrene ring, an acenaphthylene ring, a fluoranthene ring, a fluorene ring, etc.

In addition, as the aromatic in the aromatic heterocyclic groupThe heterocyclic group may be a single ring or a condensed ring. Examples of the aromatic heterocyclic group include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, imidazole, or imidazole ring having 1 free valence,

Examples of the optional substituent of the aromatic ring group 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, a halogen atom such as F, cl, br or I, a hydroxyl group, a nitro group and the like, and an alkoxy group or a hydroxyl group having 1 to 3 carbon atoms is preferable from the viewpoint of solvent solubility.

Among these, R is, from the viewpoint of sensitivity ⁷ The alkyl group is preferably an optionally substituted alkyl group, more preferably an unsubstituted alkyl group, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

(R ⁸ )

In the above formula (II), R ⁸ Represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.

R ⁸ In (1)The alkyl group may be linear, branched, or cyclic, or may be a combination thereof, but is preferably linear or branched, and more preferably branched, from the viewpoint of solvent solubility. 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, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, further preferably 4 or more, further preferably 5 or more, particularly preferably 6 or more, and most preferably 7 or more, and is preferably 12 or less, more preferably 10 or less, further preferably 9 or less, and particularly preferably 8 or less. When the number of carbon atoms of the alkyl group is not less than the lower limit, the solvent solubility tends to be good, and when the number of carbon atoms is not more than the upper limit, the sensitivity tends to be high.

Examples of the substituent optionally contained in the alkyl group 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, an alkoxycarbonyl group having 1 to 10 carbon atoms, a halogen atom such as F, cl, br or I, a hydroxyl group, etc., and an alkoxy group having 1 to 3 carbon atoms is preferable from the viewpoint of solvent solubility. From the viewpoint of sensitivity, the compound is preferably unsubstituted.

Specific examples of the alkyl group include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl and the like. Among these alkyl groups, from the viewpoint of solvent solubility, 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 even more preferable.

As R ⁸ As the aromatic ring group in (3), an aromatic ring group and an aromatic heterocyclic group are exemplified. The number of carbon atoms is usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and still more preferably 8 or less. By setting the number of carbon atoms in the aromatic ring group to the above-mentioned lower limitIn addition, when the molecular weight is not more than the above upper limit, the solubility in a solvent tends to be good.

The aromatic heterocyclic group 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 pyrrole ring, a pyrazole ring, an imidazole ring, a heterocyclic ring having 1 free valency,

Examples of the substituent optionally contained in the aromatic ring group 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, a halogen atom such as F, cl, br or I, a hydroxyl group, a nitro group and the like, and an alkoxy group or a hydroxyl group having 1 to 5 carbon atoms is preferable from the viewpoint of solubility in a solvent. The alkyl chain portion of the substituent may be straight or branched, and may further have 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.

Among these, R is R from the viewpoint of increasing the wavelength of light absorption wavelength or the like ⁸ Preferred is an optionally substituted aromatic ring group, and more preferred is an optionally substituted aromatic ring group.

(p)

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

(R ⁹ )

In the above formula (II), R ⁹ Represents an optional substituent having a valence of 1.

As the optional 1-valent substituent, there may be mentioned: alkyl groups having 1 to 10 carbon atoms such as methyl and ethyl; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; F. halogen atoms such as Cl, br, I, etc.; an acyl group having 1 to 10 carbon atoms; an alkyl ester group having 1 to 10 carbon atoms; an alkoxycarbonyl group having 1 to 10 carbon atoms; a halogenated alkyl group having 1 to 10 carbon atoms; an aromatic ring group having 4 to 10 carbon atoms; an amino group; an aminoalkyl group having 1 to 10 carbon atoms; a hydroxyl group; a nitro group; a CN group; a benzoyl group optionally having a substituent; a thienyl group optionally having a substituent, and the like. Examples of the substituent optionally contained in the benzoyl group or the thenoyl group include an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms, and the substituent may be contained in the range of 0 to 3. Among these groups, nitro and 2-thenoyl are preferable, and nitro is more preferable, from the viewpoint of increasing the absorption wavelength.

Then R ⁹ When q is 2 or more, a plurality of R ⁹ Or may be bonded to each other to form a ring. 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 above formula (II), X represents-N (R) ¹⁰ ) -or-C (R) ¹¹ )(R ¹² ) -. Of these, from the viewpoint of sensitivity, -N (R) is preferable ¹⁰ )-。

(R ¹⁰ ～R ¹² )

In the above formula (II), R ¹⁰ ～R ¹² Each independently represents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent.

R ¹⁰ ～R ¹² The alkyl group in (b) may be linear, branched or cyclic, or may be a combination thereof, but is preferably linear or branched, and more preferably linear, from the viewpoint of sensitivity.

The number of carbon atoms of the alkyl group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, further preferably 4 or more, particularly preferably 5 or more, and preferably 10 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 4 or less. When the number of carbon atoms of the alkyl group is not less than the lower limit, the solvent solubility tends to be good, and when the number of carbon atoms is not more than the upper limit, the sensitivity tends to be high.

Specific examples of the alkyl group include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl, 2-ethylhexyl, and the like. Among these alkyl groups, from the viewpoint of balance between sensitivity and solvent solubility, ethyl, propyl, isopropyl, or butyl is preferable, ethyl or propyl is more preferable, and ethyl is even more preferable.

As R ¹⁰ ～R ¹² As the aromatic ring group in (3), an aromatic ring group and an aromatic heterocyclic group are exemplified. The number of carbon atoms is usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and still more preferably 8 or less. When the number of carbon atoms in the aromatic ring group is not less than the lower limit, the molecule tends to be stable, and when the number is not more than the upper limit, the solvent solubility tends to be good.

A pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, and the like. Of these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having 1 free valence is preferable, and a benzene ring having 1 free valence is more preferable.

Examples of the optional substituent of the aromatic ring group 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, a halogen atom such as F, cl, br or I, a hydroxyl group, a nitro group and the like, and an alkoxy group or a hydroxyl group having 1 to 3 carbon atoms is preferable from the viewpoint of solvent solubility. From the viewpoint of sensitivity, the compound is preferably unsubstituted.

In addition, R ¹¹ And R ¹² The ring may be an aliphatic ring or an aromatic ring.

Of these, R is preferable from the viewpoint of sensitivity ¹⁰ ～R ¹² Each independently is an alkyl group optionally having a substituent, more preferably an unsubstituted alkyl group, and further preferably R ¹⁰ Is methyl or ethyl and R ¹¹ And R ¹² Is a butyl group.

Further, as commercially available products of the photopolymerization initiator (c 2), there can be mentioned: OXE-02 manufactured by BASF corporation, TR-PBG-304 manufactured by Changzhou powerful new electronic material corporation, TR-PBG-314, TR-PBG-358 and the like. Further, a photopolymerization initiator described in Japanese patent No. 4223071, a photopolymerization initiator described in International publication No. 2016/010036, and a photopolymerization initiator described in Japanese patent No. 5682094 can be used.

Specific examples of the photopolymerization initiator (c 2) include the following photopolymerization initiators. In the formula, nBu represents an n-butyl group.

[ chemical formula 11]

[ chemical formula 12]

[ chemical formula 13]

[ chemical formula 14]

(c) The photopolymerization initiator may further contain another photopolymerization initiator other than the photopolymerization initiator (c 1) and the photopolymerization initiator (c 2).

Examples of other photopolymerization initiators include: a metallocene compound containing a titanocene compound as described in each of Japanese patent application laid-open Nos. 59-152396 and 61-151197; hexaarylbiimidazole derivatives described in Japanese patent laid-open No. 2000-56118; halomethylation described in Japanese patent application laid-open No. 10-39503

Radical activators such as oxadiazole derivatives, halomethyl s-triazine derivatives, and N-aryl- α -amino acids such as N-phenylglycine, N-aryl- α -amino acid salts, and N-aryl- α -amino acid esters, and α -aminoalkylphenyl ketone derivatives; and oxime ester derivatives described in, for example, japanese patent application laid-open Nos. 2000-80068 and 2006-36750.

Specifically, for example, as titanocene derivatives, there can be mentioned: dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyltitanium, dicyclopentadienyl bis (2,3,4,5,6-pentafluoro-phen-1-yl) titanium, dicyclopentadienyl bis (2,3,5,6-tetrafluorophen-1-yl) titanium, dicyclopentadienyl bis (2,4,6-trifluorophen-1-yl) titanium, dicyclopentadienyl bis (2,6-difluorophen-1-yl) titanium, dicyclopentadienyl bis (2,4-difluorophen-1-yl) titanium, bis (methylcyclopentadienyl) bis (2,3,4,5,6-pentafluorophen-1-yl) titanium, bis (methylcyclopentadienyl) bis (2,6-difluorophen-1-yl) titanium, dicyclopentadienyl [2,6-difluoro-3- (pyrrol-1-yl) -phen-1-yl ] titanium, and the like.

Further, examples of the bisimidazole derivatives include: 2- (2 '-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2' -chlorophenyl) -4,5-bis (3 '-methoxyphenyl) imidazole dimer, 2- (2' -fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2 '-methoxyphenyl) -4,5-diphenylimidazole dimer, (4' -methoxyphenyl) -4,5-diphenylimidazole dimer, and the like.

In addition, as halomethylation

Oxadiazole derivatives, there may be mentioned: 2-trichloromethyl-5- (2' -benzofuranyl) -1,3,4-

Diazole, 2-trichloromethyl-5- [ beta- (2' -benzofuranyl) ethenyl]-1,3,4-

Diazole, 2-trichloromethyl-5- [ beta- (2' - (6 "-benzofuranyl) vinyl)]-1,3,4-

Diazole, 2-trichloromethyl-5-furyl-1,3,4-

Oxadiazoles, and the like.

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

Further, as α -aminoalkylphenone derivatives, there can be mentioned: 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoamylisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropylketone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like.

As oxime ester derivatives, there may be mentioned: an oxime ester compound described in, for example, JP-A-2004-534797, JP-A-2000-80068, JP-A-2006-36750, JP-A-2008-179611, JP-A-2012-526185, and JP-A2012-519191. Among them, from the viewpoint of sensitivity, methyl 4-acetoxyimino-5- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -5-oxopentanoate, and products such as OXE-01 (manufactured by BASF corporation), TR-PBG-305 (manufactured by Changzhou Qiangli corporation), NCI-930 (manufactured by ADEKA corporation) are preferable.

The other photopolymerization initiators may be used alone or in combination of two or more.

< sensitizing dye >

In order to improve the sensitivity, a sensitizing dye corresponding to the wavelength of the image exposure light source may be used in combination with the photopolymerization initiator as necessary. Examples of the sensitizing dye include xanthene dye disclosed in Japanese patent application laid-open Nos. 4-221958, 4-219756 and the like, coumarin dye having a heterocyclic ring disclosed in Japanese patent application laid-open Nos. 3-239703, 5-289335 and the like, 3-oxocoumarin compound disclosed in Japanese patent application laid-open Nos. 3-239703, 5-289335 and the like, tolylpyrrole dye disclosed in Japanese patent application laid-open No. 6-19240, and also skeleton-containing coumarin dye disclosed in Japanese patent application laid-open Nos. 47-2528, 54-155292, 45-3264 zxft 323264, 48-84183, 52-34 zxft 34, 58-3434, 58-3203-3260, 324924 and the like, as the skeleton-88027, 364124, 364924, 364138 and the like.

Among these sensitizing dyes, preferred is an amino group-containing sensitizing dye, and more preferred is a compound having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example: benzophenone compounds such as 4,4 '-dimethylaminobenzophenone, 4,4' -diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4 '-diaminobenzophenone, 3,3' -diaminobenzophenone, 3,4-diaminobenzophenone, and the like; 2- (p-dimethylaminophenyl) benzo

Azole, 2- (p-diethylaminophenyl) benzo

Azole, 2- (p-dimethylaminophenyl) benzo [4,5]Benzo (b) is

Azole, 2- (p-dimethylaminophenyl) benzo [6,7]Benzo [ b ]

Oxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-

P-dialkylaminophenyl-containing compounds such as oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, p-dimethylaminophenyl) pyridine, p-diethylaminophenyl pyridine, p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, and p-diethylaminophenyl pyrimidine。

Of these, 4,4' -dialkylaminobenzophenones are most preferred.

The sensitizing dye may be used alone or in combination of two or more.

The content of the photopolymerization initiator (c) is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, particularly preferably 4% by mass or more, and is usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 8% by mass or less, particularly preferably 6% by mass or less, relative to the total solid content of the photosensitive resin composition of the present invention. When the content of the photopolymerization initiator (c) is not less than the lower limit, the influence of oxygen inhibition tends to be suppressed, and when the content is not more than the upper limit, the substrate adhesion tends to be good.

(c) The content of the photopolymerization initiator (c 1) in the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 10% by mass or more, still more preferably 20% by mass or more, particularly preferably 30% by mass or more, and most preferably 40% by mass or more, and is preferably 99.9% by mass or less, more preferably 99% by mass or less, further preferably 90% by mass or less, and most preferably 60% by mass or less. When the content of the photopolymerization initiator (c 1) is not less than the lower limit, the internal curability tends to be good, and when the content is not more than the upper limit, the curability at the top of the pattern tends to be good.

(c) The content of the photopolymerization initiator (c 2) in the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 10% by mass or more, and most preferably 40% by mass or more, and is preferably 99.9% by mass or less, more preferably 99% by mass or less, further preferably 90% by mass or less, further preferably 80% by mass or less, and particularly preferably 60% by mass or less. When the content of the photopolymerization initiator (c 2) is not less than the lower limit, curability at the top of the pattern tends to be good, and when the content is not more than the upper limit, internal curability tends to be good.

Alkali-soluble resin (a)

The photosensitive resin composition of the present invention comprises (a) an alkali-soluble resin. (a) The alkali-soluble resin is not particularly limited as long as it changes the solubility of the exposed portion and the unexposed portion in an alkali developing solution after exposing a coating film obtained by applying and drying a photosensitive resin composition to light, and is preferably an alkali-soluble resin having an acidic functional group such as a hydroxyl group, a carboxyl group, a phosphoric group, or a sulfonic group, and more preferably an alkali-soluble resin having a carboxyl group. In addition, a resin having an ethylenically unsaturated group is 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. Specifically, epoxy (meth) acrylate resins having a carboxyl group and acrylic copolymer resins are mentioned, and more specifically, the resins described as (A1-1), (A1-2), (A2-1), (A2-2), (A2-3) and (A2-4) described later are mentioned as preferable examples, and one kind of these resins may be used, or two or more kinds thereof may be used. Among the above, the epoxy (meth) acrylate resins (A1-1) and (A1-2) having a carboxyl group are particularly preferable.

The epoxy (meth) acrylate resin having a carboxyl group is a resin obtained by further reacting a polybasic acid and/or an anhydride thereof with a hydroxyl group generated by the reaction of a reactant of an epoxy resin with an α, β -unsaturated monocarboxylic acid and/or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety. In addition, a resin obtained by reacting a polybasic acid and/or an anhydride thereof with a compound having 2 or more substituents capable of reacting with a hydroxyl group before reacting the polybasic acid and/or the anhydride thereof with the hydroxyl group, and then reacting the polybasic acid and/or the anhydride thereof with the polybasic acid is also included in the epoxy (meth) acrylate resin. Further, a resin obtained by further reacting a carboxyl group of the resin obtained in the above reaction with a compound having a functional group capable of reacting is also included in the epoxy (meth) acrylate resin.

As described above, the epoxy (meth) acrylate resin is not limited to "(meth) acrylate" because it has substantially no epoxy group in its chemical structure, but is conventionally named because it is made of an epoxy resin and is typified by "(meth) acrylate".

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) >

An alkali-soluble resin 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 then reacting with a polybasic acid and/or an anhydride thereof.

< epoxy (meth) acrylate resin (A1-2) >

An alkali-soluble resin 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 then reacting the resulting product with a polyhydric alcohol and a polybasic acid and/or an anhydride thereof.

< epoxy (meth) acrylate resin (A1-1) >

The epoxy resin used as a raw material also includes a raw material compound before forming a resin by heat curing, and the epoxy resin can be appropriately selected from known epoxy resins and used. In addition, as the epoxy resin, a compound obtained by reacting a phenolic compound with an epihalohydrin can be used. The phenolic compound is preferably a compound having a phenolic hydroxyl group having 2 or more members, and may be a monomer or a polymer.

As the kind of the epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, triphenol methane type epoxy resin, biphenol novolac type epoxy resin, naphthalene novolac type epoxy resin, epoxy resin which is a reaction product of an addition polymerization reaction product of dicyclopentadiene with phenol or cresol and epihalohydrin, adamantyl group-containing epoxy resin, fluorene type epoxy resin, and the like can be suitably used, and such epoxy resin having an aromatic ring in its main chain can be preferably used.

Specific examples of the epoxy resin include: bisphenol A-type epoxy resins (e.g., "jER (the same as registered trademark) 828", "jER1001", "jER1002", "jER1004", manufactured by Mitsubishi chemical corporation), epoxides obtained by reacting an alcoholic hydroxyl group of a bisphenol A-type epoxy resin with epichlorohydrin (e.g., "NER-1302" (epoxy equivalent 323, softening point 76 ℃ C.) manufactured by Mitsubishi chemical corporation), bisphenol F-type resins (e.g., "jER807", "EP-4001", "EP-4002", "EP-4004", manufactured by Mitsubishi chemical corporation), epoxy resins obtained by reacting an alcoholic hydroxyl group of a bisphenol F-type epoxy resin with epichlorohydrin (e.g., "NER-7406" (epoxy equivalent 350, softening point 66 ℃ C.), bisphenol S-type epoxy resins, biphenyl glycidyl ethers (e.g., "YX-4000" manufactured by mitsubishi chemical corporation), phenol novolac type epoxy resin (for example, "EPPN-201" manufactured by japan chemical corporation, "EP-152", "EP-154" manufactured by mitsubishi chemical corporation, "DEN-438" manufactured by Dow chemical corporation), ("o/m/p-) cresol novolac type epoxy resin (for example," EOCN (registered trademark) — 102S "," EOCN-1020"," EOCN-104S "manufactured by japan chemical corporation), triglycidyl isocyanurate (for example," TEPIC (registered trademark) "manufactured by japan chemical corporation), and trisphenol methane type epoxy resin (for example," EPPN (registered trademark) — 501 "manufactured by japan chemical corporation), "EPPN-502" and "EPPN-503"), alicyclic epoxy resins (Celloxide (registered trademark) 2021P and Celloxide EHPE, manufactured by cellosolve corporation), epoxy resins obtained by glycidylating phenol resins obtained by reacting dicyclopentadiene and phenol (for example, "EXA-7200" manufactured by DIC corporation and "NC-7300" manufactured by japan chemical corporation), epoxy resins represented by the following general formulae (a 1) to (a 5), and the like. Specific examples thereof include: "XD-1000" manufactured by Nippon Kabushiki Kaisha as an epoxy resin represented by the following general formula (a 1), "NC-3000" manufactured by Nippon Kabushiki Kaisha as an epoxy resin represented by the following general formula (a 2), "ESF-300" manufactured by Nippon Cinchaku Kaisha as an epoxy resin represented by the following general formula (a 4), and the like.

[ chemical formula 15]

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

[ chemical formula 16]

In the general formula (a 2), b12 represents an average value and represents 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. In addition, a plurality of R's are present in 1 molecule ²¹ May be the same or different from each other.

[ chemical formula 17]

In the general formula (a 3), X represents a linking group represented by the following general formula (a 3-1) or (a 3-2). Wherein the molecular structure contains more than 1 adamantane structure. b13 represents an integer of 2 or 3.

[ chemical formula 18]

In the above general formulae (a 3-1) and (a 3-2), R ³¹ ～R ³⁴ And R ³⁵ ～R ³⁷ Each independentlyRepresents an adamantyl group optionally having a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms optionally having a substituent, or a phenyl group optionally having a substituent. In the formula, symbol denotes a bonding position in (a 3).

[ chemical formula 19]

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

[ chemical formula 20]

In the above general formula (a 5), R ⁵¹ ～R ⁵⁴ Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, R ⁵⁵ 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, R ⁵⁶ Each independently an alkylene group having 1 to 5 carbon atoms. k is an integer of 1 to 5, l is an integer of 0 to 13, and m is each independently an integer of 0 to 5.

Among these, epoxy resins represented by any of the general formulae (a 1) to (a 5) are preferably used.

Examples of the α, β -unsaturated monocarboxylic acid or α, β -unsaturated monocarboxylic acid ester having a carboxyl group include monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o/m/p-vinylbenzoic acid, and a halogenated alkyl group, alkoxy group, halogen atom, nitro group, and cyano group-substituted compound in the α -position of (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylsalicylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2- (meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acryloyloxybutylhyiadipic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylhutylphthalic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, as the (meth) acrylic ester, an acid (anhydride) such as succinic acid (anhydride), phthalic acid (anhydride), or maleic acid (anhydride) is added to (meth) acrylic acid to give epsilon-caprolactone, and (meth) acrylates having 1 or more ethylenically unsaturated groups and 1 carboxyl group at the end, which are obtained by adding a monomer having 1 hydroxyl group at the end, such as a lactone, e.g., β -propiolactone, γ -butyrolactone, or δ -valerolactone, a monomer having 1 hydroxyl group at the end, such as hydroxyalkyl (meth) acrylate, or a compound having 1 hydroxyl group at the end, such as pentaerythritol tri (meth) acrylate. Further, (meth) acrylic acid dimer and the like can be cited.

Among these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.

As a method for adding an α, β -unsaturated monocarboxylic acid or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known method can be used. For example, an α, β -unsaturated monocarboxylic acid or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group may be reacted with an epoxy resin in the presence of an esterification catalyst at a temperature of 50 to 150 ℃. Examples of the esterification catalyst used herein include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride.

The epoxy resin, the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used singly or in combination of two or more.

The amount of the α, β -unsaturated monocarboxylic acid or α, β -unsaturated monocarboxylic acid ester having a carboxyl group to be used is preferably in the range of 0.5 to 1.2 equivalents, and more preferably in the range of 0.7 to 1.1 equivalents, relative to 1 equivalent of the epoxy group of the epoxy resin.

When the amount of the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group is equal to or more than the above lower limit, the amount of the unsaturated group introduced becomes sufficient, the subsequent reaction with a polybasic acid and/or an acid anhydride thereof becomes sufficient, and the residual epoxy group tends to be suppressed. On the other hand, when the amount is less than the upper limit value, the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group tends to be inhibited from remaining as an unreacted product and deteriorating the curing properties.

Examples of the polybasic acid and/or the anhydride thereof include: 1 or 2 or more selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylene tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyl tetracarboxylic acid, and acid anhydrides thereof.

Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides of these acids are preferred. Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

The addition reaction of the polybasic acid and/or the anhydride thereof may be continued by a known method under the same conditions as the addition reaction of the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group to the epoxy resin to obtain the desired product. The amount of the polybasic acid and/or the acid anhydride component thereof added is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150mgKOH/g, and more preferably such that the acid value is in the range of 20 to 140 mgKOH/g. When the acid value of the carboxyl group-containing epoxy (meth) acrylate resin is not less than the lower limit, the alkali developability tends to be good, and when the acid value is not more than the upper limit, the curability tends to be good.

< Synthesis of (A1-1) resin and Synthesis of (A1-2) resin having branched structure introduced by adding polyol to (A1-1) resin >

A polyhydric alcohol such as trimethylolpropane, pentaerythritol, dipentaerythritol, or the like may be added to the resin (A1-1) during the synthesis of the resin by addition reaction of the polybasic acid and/or the acid anhydride thereof to introduce a multi-branched structure.

The carboxyl group-containing epoxy (meth) acrylate resin can be obtained by mixing a polybasic acid and/or an anhydride thereof with a reactant of an epoxy resin and an α, β -unsaturated monocarboxylic acid or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group, or by mixing a polybasic acid and/or an anhydride thereof and a polyhydric alcohol with a reactant of an epoxy resin and an α, β -unsaturated monocarboxylic acid or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group, and then heating the mixture. In this case, the mixing order of the polybasic acid and/or anhydride thereof and the polyhydric alcohol is not particularly limited. Upon warming, the polybasic acid and/or anhydride thereof undergoes an addition reaction with any hydroxyl group present in the mixture of the reactant of the epoxy resin with the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group and the polyhydric alcohol.

The carboxyl group-containing epoxy (meth) acrylate resin may be used alone or in combination of two or more kinds.

The amount of the polyol used is usually about 0.01 to 0.5 times by mass, preferably about 0.02 to 0.2 times by mass, based on the reaction product of the epoxy resin component and the α, β -unsaturated monocarboxylic acid ester component having a carboxyl group in the α, β -unsaturated monocarboxylic acid or ester moiety, from the viewpoint of suppressing thickening and gelation and exhibiting the effect.

The acid value of the epoxy (meth) acrylate resin (A1-1) or (A1-2) obtained in this way is usually not less than 10mgKOH/g, preferably not less than 50mgKOH/g, more preferably not less than 70mgKOH/g, still more preferably not less than 90mgKOH/g, and furthermore preferably not more than 200mgKOH/g, more preferably not more than 150mgKOH/g, still more preferably not more than 120 mgKOH/g. When the acid value of the resin is not less than the lower limit, the developability tends to be good, and when the acid value is not more than the upper limit, the alkali resistance tends to be good.

The weight average molecular weight (Mw) of the epoxy (meth) acrylate resins (A1-1) and (A1-2) as measured by Gel Permeation Chromatography (GPC) and converted to polystyrene is preferably 1,000 or more, more preferably 1,500 or more. 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 particularly preferably 6,000 or less. When the weight average molecular weight (Mw) is not less than the lower limit, sensitivity, coating strength, and alkali resistance tend to be good, and when the weight average molecular weight (Mw) is not more than the upper limit, developability and resolubility tend to be good.

< acrylic copolymer resin (A2-1), (A2-2), (A2-3), (A2-4) >

As the acrylic copolymer resin, various polymer compounds described in, for example, japanese patent application laid-open Nos. 7-207211, 8-259876, 10-300922, 11-140144, 11-174224, 2000-56118, 2003-233179, and 2007-270147 are used, and the following resins (A2-1) to (A2-4) are preferable, and among them, a resin (A2-1) is particularly preferable.

(A2-1): a resin obtained by adding an unsaturated monobasic acid to at least a part of epoxy groups of a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, or a resin obtained by adding a polybasic acid anhydride to at least a part of hydroxyl groups generated by the addition reaction

(A2-2): straight-chain alkali-soluble resin having carboxyl group in main chain

(A2-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group part of the resin (A2-2)

(A2-4): (meth) acrylic resin

From the viewpoint of sensitivity, the photosensitive resin composition of the present invention preferably further contains at least one of (A1-1), (A1-2), (A2-1), and (A2-3) as the ethylenically unsaturated group-containing alkali-soluble resin. In the photosensitive resin composition of the present invention, it is particularly preferable to contain at least one of (A1-1) and (A1-2) as the epoxy (meth) acrylate resin as the ethylenically unsaturated group-containing alkali-soluble resin from the viewpoint of surface curability.

Other alkali-soluble resins may be used in combination in the photosensitive resin composition of the present invention.

The other alkali-soluble resin is not limited, and may be selected from resins generally used in photosensitive resin compositions for color filters. Examples thereof include alkali-soluble resins described in, for example, japanese patent application laid-open Nos. 2007-271727, 2007-316620 and 2007-334290.

The content of the alkali-soluble resin (a) is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, and still more preferably 30% by mass or less, based on the total solid content of the photosensitive resin composition of the present invention. When the content ratio of the alkali-soluble resin (a) is not less than the lower limit, solubility of the unexposed portion in the developer tends to be good, and when the content ratio is not more than the upper limit, excessive penetration of the developer into the exposed portion can be suppressed, and image clarity and adhesion tend to be good.

As described above, in the photosensitive resin composition of the present invention, the alkali-soluble resin (a) preferably contains at least one of the above-described (A1-1), (A1-2), (A2-1), (A2-2), (A2-3), and (A2-4), and when other alkali-soluble resins are contained, the content ratio thereof is 20 mass% or less, preferably 10 mass% or less, with respect to the total of the alkali-soluble resins (a).

[ b ] photopolymerizable monomer >

The photosensitive resin composition of the present invention contains (b) a photopolymerizable monomer in view of sensitivity and the like.

Examples of the photopolymerizable monomer (b) used in the present invention include: a compound having at least 1 ethylenically unsaturated group in the molecule (hereinafter also referred to as "ethylenic monomer"). Specific examples thereof include: and esters of (meth) acrylic acid, alkyl (meth) acrylates, acrylonitrile, styrene, and carboxylic acids having 1 ethylenically unsaturated bond with polyhydric or monohydric alcohols.

In the present invention, a polyfunctional ethylenic monomer having 2 or more ethylenically unsaturated groups in 1 molecule is particularly preferably used. 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, further preferably 5 or more, and particularly preferably 6 or more, and usually 10 or less, preferably 8 or less. When the number of ethylenically unsaturated groups is not less than the lower limit, the photosensitive resin composition tends to have high sensitivity, and when the number is not more than the upper limit, curing shrinkage during polymerization tends to be small.

Examples of polyfunctional olefinic monomers include, for example: esters of aliphatic polyols with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; esters obtained by esterification of a polyhydric hydroxyl compound such as an aliphatic polyhydric compound or an aromatic polyhydric compound with an unsaturated carboxylic acid or a polycarboxylic acid.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include: acrylic esters of aliphatic polyhydric compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, methacrylic esters obtained by replacing the acrylic esters of these exemplified compounds with methacrylic esters, itaconic esters similarly obtained by replacing the acrylic esters of these exemplified compounds with itaconic esters, crotonic esters obtained by replacing crotonic esters, and maleic esters obtained by replacing the acrylic esters with maleic esters.

As the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, there may be mentioned: and acrylates and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate and pyrogallol triacrylate.

The esters obtained by esterification of polycarboxylic acids and unsaturated carboxylic acids with polyhydric hydroxyl compounds are not necessarily a single substance, and representative examples thereof include: condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerol, and the like.

Further, as examples of the polyfunctional olefinic monomer used in the present invention, urethane (meth) acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate or a polyol and a hydroxyl group-containing (meth) acrylate; such epoxy acrylates as addition reaction products of a polyhydric epoxy compound with hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are useful.

These monomers may be used alone or in combination of two or more.

The content of the (b) 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% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10% by mass or less, relative to the total solid content of the photosensitive resin composition. When the content of the photopolymerizable monomer is less than the above upper limit, the permeability of the developing solution into the exposed portion tends to be 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 the amount is not less than the lower limit, the photocuring by ultraviolet irradiation tends to be improved and the alkali developability tends to be good.

The mass ratio of the content ratio of the alkali-soluble resin (a) to the content ratio of the photopolymerizable monomer (b) in the photosensitive resin composition of the present invention is usually 0.5 or more, preferably 1 or more, more preferably 2 or more, and further preferably 2.5 or more, and is usually 15 or less, preferably 10 or less, more preferably 8 or less, and further preferably 5 or less. When the amount is equal to or more than the lower limit, the curing shrinkage during curing tends to be small, and when the amount is equal to or less than the upper limit, the hardness of the cured film tends to be increased.

Color material (d)

The photosensitive resin composition of the present invention contains a coloring material when used for formation of a pixel of a color filter, a black matrix, a colored spacer, and the like. The coloring material is a material for coloring the photosensitive resin composition of the present invention. As the coloring material, a dye or a pigment can be used, but a pigment is preferable in terms of heat resistance, light resistance, and the like.

Examples of pigments include: various color pigments such as blue pigment, green pigment, red pigment, yellow pigment, violet pigment, orange pigment, brown pigment, and black pigment. The structure of the compound includes azo compounds, phthalocyanine compounds, quinacridone compounds, benzimidazolone compounds, isoindolinone compounds, and bis-indolinone compounds

Organic pigments such as oxazines, indanthrene and perylene, and various inorganic pigments may be mentioned.

Specific examples of pigments that can be used in the present invention are shown below by the pigment numbers. Note that the terms "c.i. pigment red 2" and the like listed below refer to the pigment reference number (c.i.).

As the red pigment, there can be mentioned: c.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. Among them, c.i. pigment red 48, 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254 are preferable, and c.i. pigment red 177, 209, 224, 254 are more preferable.

Examples of the blue pigment include: c.i. pigment blue 1, 1:2, 9, 14, 15. Among them, c.i. pigment blue 15, 15.

As the green pigment, there can be mentioned: c.i.

pigment green

1,2,4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58. Among them, c.i. pigment green 7, 36 and 58 are preferably listed.

As the yellow pigment, there can be mentioned: c.i. pigment yellow 1, 1:1, 2,3,4,5,6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 1, 36: 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, 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. Among them, c.i. pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 are preferable, and c.i. pigment yellow 83, 138, 139, 150, 180 are more preferable.

As orange pigments, mention may be made of: c.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. Among them, c.i. pigment orange 38, 71 can be preferably cited.

As the violet pigment, there can be mentioned: pigment violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Among them, c.i. pigment violet 19 and 23 are preferable, and c.i. pigment violet 23 is more preferable.

In the case where the photosensitive resin composition of the present invention is a photosensitive resin composition for a resin black matrix of a color filter, a black color material can be used as the color material (d). The black color material may be a single black color material or a mixture of red, green, blue, and the like. These color materials may be appropriately selected from inorganic or organic pigments and dyes.

Examples of the color materials that can be used in combination to prepare a black color material include: victoria pure blue (42595), basic Sophora yellow O (41000), cationic brilliant yellow (basic brilliant yellow) (basic 13), rhodamine 6GCP (45160), rhodamine B (45170), safranin OK70:100 (50240), papaver red X (42080), no. 120/Lei Ao Noel yellow (21090), lei Ao Noel yellow GRO (21090), schlemlerian fast yellow 8GF (21105), benzidine yellow 4T-564D (3926 zxf3926), schlemlerian fast red 4015 (12355), lei Ao Noel red 7B4401 (15850), fasttogen blue TGR-L (74160), 3835 zxft Noel blue (SM 50), 3924 zxft Blue ES (pigment blue 15), lionogen blue O (35168D), and Nonoz red () with the aforementioned numbers for pigment numbers of pigments C.34, and others, and they are the numbers of pigment numbers of Nonox blue No. GD 3534, no..

Further, as other pigments which can be used in combination, there can be mentioned, for example, the following pigments, if they are represented by c.i. symbol: c.i. yellow pigment 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, c.i. orange pigment 36, 43, 51, 55, 59, 61, c.i. red pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, c.i. violet pigment 19, 23, 29, 30, 37, 40, 50, c.i. blue pigment 15, 15.

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, xeronine black, titanium black, perylene black, lactam black, and the like.

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

Mitsubishi chemical corporation: MA7, MA77, MA8, MA11, MA100R, MA, 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, # 3562 zxft 359B, OIL B, OIL, B, OIL B

Manufactured by Degussa: printex (registered trademark, the same below) 3, printex3OP, printex30OP, printex40, printex45, printex55, printex60, printex75, printex80, printex85, printex90, printex A, printex L, printex G, printex P, printex U, printex V, printex G, specialBlack550, specialBlack350, specialBlack250, specialBlack100, specialBlack6, specialBlack5, specialBlack4, color Black FW1, color Black FW2, color FW2V, color Black FW18, color Black 200, color S160, color S170

Manufactured by Cabot corporation: monarch (registered trademark, the same below) 120, monarch280, monarch460, monarch800, monarch880, monarch900, monarch1000, monarch1100, monarch1300, monarch1400, monarch4630, REGAL (registered trademark, the same below) 99, REGAL99R, REGAL415, REGAL415R, REGAL, REGAL250R, REGAL330, REGAL400R, REGAL R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark) 72 XC R, ELFTEX (registered trademark) -8

Manufactured by Birror corporation: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN 4324 zxft 431170, RAVEN1190 3245 zxft 321250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

As examples of other black pigments, titanium black, aniline black, and iron oxide-based black pigments, and organic pigments of three colors of red, green, and blue may be mixed and used as the black pigment.

Further, as the pigment, barium sulfate, lead sulfate, titanium oxide, lead yellow, red iron oxide, chromium oxide, or the like can be used. A plurality of the above-mentioned pigments may be used in combination. For example, a green pigment may be used in combination with a yellow pigment, or a blue pigment may be used in combination with a violet pigment, in order to adjust the chroma.

The average particle size of the pigment usable in the present invention is not particularly limited as long as it is an average particle size capable of displaying a desired color when a colored layer of a color filter is formed, and varies depending on the type of the pigment used, but is preferably within a range of 10 to 100nm, more preferably within a range of 10 to 70 nm. When the average particle diameter of the pigment is in the above range, the color characteristics of a liquid crystal display device manufactured using the photosensitive resin composition of the present invention tend to be high in quality.

When the pigment is carbon black, the average particle diameter is preferably 60nm or less, more preferably 50nm or less, and further preferably 20nm or more. When the average particle diameter is not more than the upper limit, scattering is reduced, and deterioration of color characteristics such as light-shielding property and contrast tends to be suppressed. Further, when the average particle diameter is not less than the lower limit, the amount of the dispersant does not need to be excessively increased, and the dispersibility tends to be good.

The average particle diameter of the pigment can be determined by directly measuring the size of the primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle are measured, and the average value thereof is taken as the particle diameter of the particle thereof. Next, for 100 or more particles, the volume (weight) of each particle was determined by approximating it to a rectangular parallelepiped of the determined particle diameter, and the volume average particle diameter was determined as the average particle diameter. In the case of an electron microscope, the same result can be obtained using either a transmission Type (TEM) or a scanning type (SEM).

The photosensitive resin composition of the present invention preferably contains at least a pigment, and a dye may be used in combination within a range not affecting the effects of the present invention. As dyes that can be used in combination, there are listed: azo dyes, anthrone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like.

As azo dyes, there may be mentioned, for example: c.i. acid yellow 11, c.i. acid orange 7, c.i. acid red 37, c.i. acid red 180, c.i. acid blue 29, c.i. direct red 28, c.i. direct red 83, c.i. direct yellow 12, c.i. direct orange 26, c.i. direct green 28, c.i. direct green 59, c.i. active yellow 2, c.i. active red 17, c.i. active red 120, c.i. active black5, c.i. disperse orange 5, c.i. disperse red 58, c.i. disperse blue 165, c.i. basic blue 41, c.i. basic red 18, c.i. medium red 7, c.i. medium yellow 5, c.i. medium black 7, etc.

Examples of the anthrone dyes include: c.i. vat blue 4, c.i. acid blue 40, c.i. acid green 25, c.i. active blue 19, c.i. active blue 49, c.i. disperse red 60, c.i. disperse blue 56, c.i. disperse blue 60, etc.

Further, as phthalocyanine-based dyes, for example: c.i. vat blue 5, etc.; examples of the quinoneimine-based dye include: c.i. basic blue 3, c.i. basic blue 9, and the like; examples of quinoline dyes include: c.i. solvent yellow 33, c.i. acid yellow 3, c.i. disperse yellow 64, and the like; examples of the nitro dye include: c.i. acid yellow 1, c.i. acid orange 3, c.i. disperse yellow 42, and the like.

The content ratio of the color material (d) to the total solid content in the photosensitive resin composition can be selected generally within the range of 1 to 70% by mass. In this range, the content is more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, and still more preferably 60% by mass or less.

The photosensitive resin composition of the present invention can be used for various applications as described above, but is particularly effective in the case of being used for forming a black matrix for a color filter, because of its excellent image formability. In the case of forming a black matrix, the above-described black color material such as carbon black or titanium black, or a mixture of a plurality of color materials other than black color may be used as the color material (d) to adjust the color to black. Among these, carbon black is particularly preferably used from the viewpoint of dispersion stability and light-shielding properties.

The present invention is particularly effective in a region where the pigment concentration of the black pigment is large. In particular, in recent years, the black pigment concentration has been required to be high in order to increase the light-shielding degree. The content ratio of the black pigment in the region where such an effect is significant is 40% by mass or more, preferably 45% by mass or more, and more preferably 50% by mass or more, based on the entire solid content of the photosensitive resin composition.

By adjusting the content of the black pigment in the photosensitive resin composition to be within the above range, a photosensitive resin composition having high light-shielding properties (optical density, OD value) can be obtained. Specifically, when the content of the black pigment is 45% by mass or more, the optical density in the case of forming a black matrix having a thickness of 1 μm by using the photosensitive resin composition of the present invention can be set to a value of 4.0 or more. The optical density is more preferably 4.2 or more. In the region having high light-shielding property, ultraviolet rays are difficult to transmit to deep portions, and crosslinking by photopolymerization becomes weak particularly in portions where the substrate and the thin wires are in close contact, but when the photosensitive resin composition of the present invention is used, particularly when the content ratio of the black pigment is large, the effects of the present invention can be clearly confirmed. The content of the black pigment is particularly effective in the range of 40 to 65% by mass. When the content ratio of the black pigment is equal to or higher than the lower limit, the film thickness tends to be suppressed from becoming excessively large with respect to the color density, and when the content ratio is equal to or lower than the upper limit, sufficient image formability tends to be easily ensured.

The content of the coloring material (d) in the photosensitive resin composition is usually 20 parts by mass or more, preferably 30 parts by mass or more, more preferably 40 parts by mass or more, further preferably 60 parts by mass or more, further preferably 80 parts by mass or more, particularly preferably 120 parts by mass or more, and most preferably 160 parts by mass or more, and usually 500 parts by mass or less, preferably 300 parts by mass or less, and more preferably 280 parts by mass or less, per 100 parts by mass of the alkali-soluble resin (a). When the content ratio of the color material (d) is equal to or higher than the lower limit, the solubility of the unexposed area in the developer tends to be easily reduced, and when the content ratio is equal to or lower than the upper limit, a desired image film thickness tends to be easily obtained.

[ dispersant (e) >

In the present invention, it is important to finely disperse the color material and stabilize the dispersed state thereof to ensure the stability of quality, and therefore (e) a dispersant is preferably contained.

The dispersant is preferably a polymer dispersant having a functional group, and further preferably a carboxyl group from the viewpoint of dispersion stability; a phosphate group; a sulfonic acid group; or a salt group thereof; primary, secondary or tertiary amino groups; quaternary ammonium salt groups; a polymer dispersant derived from a functional group such as a nitrogen-containing heterocyclic group such as pyridine, pyrimidine or pyrazine. Among them, those having a primary amino group, a secondary amino group or a tertiary amino group are particularly preferable; quaternary ammonium salt groups; a polymer dispersant derived from a basic functional group such as a nitrogen-containing heterocyclic group such as pyridine, pyrimidine or pyrazine. By using such a polymer dispersant having a basic functional group, the dispersibility tends to be good and a high light-shielding property tends to be achieved.

Examples of the polymeric dispersant include: urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of an amino group-containing monomer and a macromonomer, polyoxyethylene alkyl ether 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-Chemicals b.v. (EFKA)), disperbyk (registered trademark, manufactured by BYK-Chemie), disparlon (registered trademark, manufactured by nakeh chemical co., ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by shin-shiko chemical industries co., ltd.), teflon or Floren (registered trademark, manufactured by cohno chemical co., ltd.), ajisper (registered trademark, manufactured by Ajinomoto Fine-Techno).

These polymeric dispersants may be used alone or in combination of two or more.

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

The weight average molecular weight (Mw) of the polymeric dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less, more preferably 30,000 or less. When the weight average molecular weight (Mw) is not more than the upper limit, the alkali developability tends to be good even when the pigment concentration is high.

Examples of the urethane and acrylic polymer dispersants include: DISPERBYK-160-167, 182 series (all carbamates), DISPERBYK-2000,2001 and the like (all acrylics) (both manufactured by BYK-Chemie). Among the above-mentioned urethane-based polymer dispersants having a basic functional group and a polyester and/or polyether bond, preferable polymer dispersants having a weight average molecular weight of 30,000 or less include DISPERBYK-167 and 182.

< urethane Polymer dispersing agent >

Specific examples of the preferable chemical structure as the urethane-based polymer dispersant include: a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting a polyisocyanate compound, a compound having 1 or 2 hydroxyl groups in the molecule and a compound having 1 active hydrogen and a tertiary amino group in the same molecule, and the like.

Examples of the polyisocyanate compounds include: aromatic diisocyanates such as p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4' -diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and dimethylbiphenyl diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanates such as dimer acid diisocyanate, isophorone diisocyanate, 4,4' -methylene bis (cyclohexyl isocyanate), alicyclic diisocyanates such as ω, ω ' -diisocyanate dimethylcyclohexane, xylylene diisocyanate, aliphatic diisocyanates having aromatic rings such as α, α, α ', α ' -tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, dicyclohexylmethane triisocyanate, and triisocyanate (phenyl) trisisocyanate, phosphoric acid ester such as triphenyl phosphate, and hydrogenated adducts thereof. The polyisocyanate is preferably a trimer of an organic diisocyanate, and most preferably a trimer of toluene diisocyanate and a trimer of isophorone diisocyanate. These compounds may be used alone or in combination of two or more.

Examples of the method for producing the isocyanate trimer include the following methods: the polyisocyanate is partially trimerized with an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc., and after the trimerization is stopped by adding a catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin film distillation to obtain the intended isocyanurate group-containing polyisocyanate.

Examples of the compound having a number average molecular weight of 300 to 10,000 and having 1 or 2 hydroxyl groups in the same molecule include: polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and compounds obtained by alkoxylating one-side terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms, and mixtures of two or more of these.

Examples of polyether diols include: polyether glycol, polyether ester glycol, and a mixture of two or more thereof. As the polyether diol, there may be mentioned: polyether glycols obtained by homopolymerizing or copolymerizing alkylene oxides, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and mixtures of two or more thereof.

As the polyether ester diol, there may be mentioned: polyether ester diols obtained by reacting a diol containing an ether group or a mixture of other diols with a dicarboxylic acid or an anhydride thereof, or a polyester diol with an alkylene oxide, such as poly (polyoxytetramethylene) adipate, and the like. The polyether glycol is most preferably polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound obtained by alkoxylating one terminal hydroxyl group of one of these compounds with an alkyl group having 1 to 25 carbon atoms.

As the polyester diol, there may be mentioned: aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-3535 zxft 35-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 3256 zxft 56-trimethyl-1,3-pentanediol, 5623-hexanediol, 2-methyl-2,4-pentanediol, 3256 zxft-3456-trimethyl-3456-pentanediol, 34zxft 5738, ethylene glycol, N-345749, N-methyl-xylene glycol, N-ethylene glycol, N-345749, N-ethylene glycol, N-345776, N-methyl-xylene glycol, N-ethylene glycol, N-345749, N-xylene glycol, etc. aliphatic diols, and the like are polycondensed to obtain aliphatic diols such as aliphatic diols: polyethylene glycol adipate, polybutylene adipate, 1,6-hexanediol adipate, polyethylene glycol adipate/propylene glycol ester, and the like, or polylactone diols or polylactone monools obtained by using the above-mentioned diols or monools having 1 to 25 carbon atoms as an initiator, for example: polycaprolactone diol, polymethylvalerolactone, and mixtures of two or more thereof. The polyester diol is most preferably polycaprolactone diol or polycaprolactone monool obtained by using an alcohol having 1 to 25 carbon atoms as an initiator.

As the polycarbonate diol, there may be mentioned: 1,6-hexanediol polycarbonate, 3-methyl-1,5-pentylene carbonate, and the like; as the polyolefin diol, there may be mentioned: polybutadiene diol, hydrogenated polyisoprene diol, and the like.

These compounds may be used alone or in combination of two or more.

The number average molecular weight of the compound having 1 or 2 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.

The compounds having 1 active hydrogen and a tertiary amino group in the same molecule which can be used in the present invention will be described. As active hydrogen, i.e., a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, there can be mentioned: among the hydrogen atoms in the functional groups such as hydroxyl, amino, thiol and the like, the hydrogen atom of an amino group is preferable, and the hydrogen atom of a primary amino group is particularly 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, more specifically, an imidazole ring or a triazole ring.

Examples of such a compound having an active hydrogen and a tertiary amino group in the same molecule include: n, N-dimethyl-1,3-propanediamine, N-diethyl-1,3-propanediamine, N-dipropyl-1,3-propanediamine, N-dibutyl-1,3-propanediamine, N-dimethylethylenediamine, N-diethylethylenediamine, N, N-dipropylethylenediamine, N-dibutylethylenediamine, N-dimethyl-1,4-butanediamine, N-diethyl-1,4-butanediamine, N-dipropyl-1,4-butanediamine, N-dibutyl-1,4-butanediamine, and the like.

In addition, examples of the nitrogen-containing heterocycle in the case where the tertiary amino group has a nitrogen-containing heterocycle structure include: pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring

Nitrogen-containing five-membered heterocyclic rings such as an azole ring, a benzothiazole ring, and a benzothiadiazole ring, and nitrogen-containing six-membered heterocyclic rings such as a pyridine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an acridine ring, and an isoquinoline ring. Preferred among these nitrogen-containing heterocycles are imidazole rings or triazole rings.

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. In addition, as specific examples of the compound having a triazole ring and an amino group, there can be mentioned: 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole, and the like. Among them, N-dimethyl-1,3-propanediamine, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole and 3-amino-1,2,4-triazole are preferable.

These compounds may be used alone or in combination of two or more.

The preferable blending ratio of the raw materials for producing the urethane polymer dispersant is 10 to 200 parts by mass, preferably 20 to 190 parts by mass, and more preferably 30 to 180 parts by mass of a compound having a number average molecular weight of 300 to 10,000 and having 1 or 2 hydroxyl groups in the same molecule, and 0.2 to 25 parts by mass, and preferably 0.3 to 24 parts by mass of a compound having active hydrogen and a tertiary amino group in the same molecule, based on 100 parts by mass of the polyisocyanate compound.

The urethane polymer dispersant can be produced by a known method for producing a polyurethane resin. As the solvent in the production, generally used are: ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate and cellosolve acetate, hydrocarbons such as benzene, toluene, xylene and hexane, partial alcohols such as diacetone alcohol, isopropyl alcohol, sec-butyl alcohol and tertiary alcohol, chlorides such as dichloromethane and chloroform, ethers such as tetrahydrofuran and diethyl ether, aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide, and the like. These solvents may be used alone or in combination of two or more.

In the above production, a urethane reaction catalyst is usually used. Examples of the catalyst include: 1 or more than 2 kinds of tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and stannous octoate, iron compounds such as iron acetylacetonate and iron chloride, tertiary amines such as triethylamine and triethylenediamine, and the like.

< method for measuring amine number >

The tertiary amine value of the dispersant is represented by the mass of KOH equivalent to the amount of base per 1g of solid content other than the solvent in the dispersant sample, and can be measured by the following method.

0.5 to 1.5g of a dispersant sample was precisely weighed in a100 mL beaker and dissolved in 50mL of acetic acid. The solution was subjected to 0.1mol/L of HClO using an automatic titration apparatus equipped with a pH electrode ₄ The (perchloric) acetic acid solution was subjected to neutralization titration. The amine value was determined according to the following equation, with the inflection point of the titration pH curve as the titration end point.

Amine value [ mgKOH/g ] = (561 XV)/(W.times.S)

[ wherein, W: represents the weighed amount [ g ] of the dispersant sample, V: the titration amount at the end of titration [ mL ], S: the solid content concentration of the dispersant sample is shown as mass%. ]

The amount of the compound having an active hydrogen and a tertiary amino group introduced into the same molecule is preferably controlled in the range of 1 to 100mgKOH/g, more preferably 5 to 95mgKOH/g, in terms of the amine value after the reaction. The amine value is a value corresponding to an acid value in mg of KOH by neutralization titration of a basic amino group with an acid. When the amine value is equal to or higher than the lower limit, the dispersibility tends to be good, and when the amine value is equal to or lower than the upper limit, the developability tends to be good.

When an isocyanate group remains in the polymer dispersant in the above reaction, it is preferable to further destroy the isocyanate group with an alcohol or an amino compound because the stability of the product with time can be improved.

The weight average molecular weight (Mw) of the urethane polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. The weight average molecular weight (Mw) of the urethane polymer dispersant is particularly preferably 30,000 or less. When the weight average molecular weight (Mw) is equal to or higher than the lower limit, dispersibility and dispersion stability tend to be good, and when the weight average molecular weight (Mw) is equal to or lower than the upper limit, solubility tends to be good and dispersibility also tends to be good. When the molecular weight is 30,000 or less, alkali developability tends to be good particularly at a high pigment concentration. Examples of such particularly preferred commercially available urethane dispersants include DISPERBYK-167 and 182 (BYK-Chemie).

The content of the dispersant (e) in the entire solid content of the photosensitive resin composition is usually 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, particularly preferably 10% by mass or less, and usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 7% by mass or more. The content of the dispersant is usually 5 parts by mass or more, preferably 10 parts by mass or more, and usually 200 parts by mass or less, preferably 80 parts by mass or less, more preferably 50 parts by mass or less, further preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less, based on 100 parts by mass of the (d) color material. When the content of the dispersant is not less than the lower limit, sufficient dispersibility tends to be easily ensured, and when the content is not more than the upper limit, color density, sensitivity, film-forming property, and the like tend to be easily made sufficient without decreasing the ratio of other components.

In particular, the dispersant is preferably a polymer dispersant and a pigment derivative (dispersing aid) are used in combination, and in this case, the content of the pigment derivative is usually 0.1% by mass or more, preferably 0.5% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less, and more preferably 2% by mass or less, relative to the total solid content of the photosensitive resin composition of the present invention.

< thiols >

In order to achieve high sensitivity and improve adhesion to a substrate, the photosensitive resin composition of the present invention preferably contains a thiol group. Examples of the thiol group include: hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol dimercaptopropionate, butanediol dimercaptoacetate, ethylene glycol dimercaptoacetate, trimethylolpropane trimercaptoacetate, butanediol dimercaptopropionate, trimethylolpropane trimercaptopropionate, trimethylolpropane trimercaptoacetate, pentaerythritol tetramercaptopropionate, pentaerythritol tetramercaptoacetate, trihydroxyethyl trimercaptopropionate, ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate) (abbreviated as PGMB), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane; (trade name; manufactured by Karenz MT BD1, showa Denko K.K.), butanediol trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate); (trade name; manufactured by Karenz MT PE1, showa Denko K.K.), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptobutyrate) (abbreviated to TPMB), trimethylolpropane tris (2-mercaptoisobutyrate) (abbreviated to TPMIB), 1,3,5-tris (3-mercaptobutoxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione; (trade name; manufactured by Karenz MT NR1, showa Denko K.K.), and these thiols may be used alone in 1 of each kind or in a mixture of 2 or more kinds. The above-mentioned polyfunctional thiol such as PGMB, TPMB, TPMIB, karenz MT BD1, karenz MT PE1 or Karenz MT NR1 is preferable, among which Karenz MT BD1, karenz MT PE1 or Karenz MT NR1 is more preferable, and Karenz MT PE1 is particularly preferable.

When the thiol compound is used, the content of the thiol compound is usually 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less, based on the entire solid content of the photosensitive resin composition of the present invention. When the content ratio of the thiol compound is not less than the lower limit, the sensitivity reduction tends to be suppressed, and when the content ratio is not more than the upper limit, the storage stability tends to be improved.

< solvent >

The photosensitive resin composition of the present invention is usually used in a state in which (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, (d) a color material, and various materials used as needed are dissolved or dispersed in an organic solvent.

The organic solvent is preferably selected to have a boiling point (the same applies hereinafter to all boiling points under the conditions of pressure 1013.25[ hPa ]) in the range of 100 to 300 ℃, and more preferably to have a boiling point of 120 to 280 ℃.

Examples of such an organic solvent include the following organic solvents.

Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-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 monoethyl ether, and tripropylene glycol methyl ether;

glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol ethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;

glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxyamyl 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 monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

glycol diacetate esters such as ethylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, and the like;

alkyl acetates such as cyclohexanol acetate;

ethers such as amyl ether, ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether;

ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl amyl ketone;

monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;

aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl;

aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

linear or cyclic esters such as amyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl decanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ -butyrolactone;

alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

halogenated hydrocarbons such as chlorobutane and chloropentane;

ether ketones such as methoxymethylpentanone;

nitriles such as acetonitrile and benzonitrile.

Examples of commercially available solvents that meet the above-mentioned requirements include: mineral spirits (Mineral spirits), varsol #2, apco #18solvent, apco trinner, sonal solvent nos. 1 and 2, solvesso #150, shell TS28solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("cellosolve" is a registered trademark, the same applies hereinafter), ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether (diglyme) (both trade names), and the like.

These organic solvents may be used alone, or 2 or more kinds thereof may be used in combination.

When the pixels of the color filter or the black matrix are formed by photolithography, it is preferable to select an organic solvent having a boiling point in the range of 100 to 250 ℃. More preferably an organic solvent having a boiling point of 120 to 230 ℃.

Among the above organic solvents, glycol alkyl ether acetates are preferable in terms of good balance of coatability, surface tension, and the like and high solubility of the constituent components in the composition.

In addition, the glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As other organic solvents which can be used in combination, glycol monoalkyl ethers are particularly preferred. Among these, propylene glycol monomethyl ether is preferred in view of the solubility of the components in the composition. The diol monoalkyl ethers are preferably 5 to 30 mass%, more preferably 5 to 20 mass%, in view of the tendency that the pigment is likely to aggregate and the storage stability of the photosensitive resin composition to be obtained is lowered, for example, the viscosity of the photosensitive resin composition to be obtained is increased when the polarity of the diol monoalkyl ethers is high and the amount of the diol monoalkyl ethers added is too large.

In addition, it is also preferable to use an organic solvent having a boiling point of 200 ℃ or higher (hereinafter also referred to as "high-boiling solvent") in combination. The combined use of such high boiling point solvents makes the photosensitive resin composition less likely to dry, but has the effect of preventing the uniform dispersion state of the pigment in the composition from being broken by rapid drying. That is, for example, the effect of preventing the occurrence of foreign matter defects due to precipitation or solidification of color materials or the like at the tip of the slit nozzle is obtained. From the viewpoint of remarkable effects, among the various solvents described above, dipropylene glycol methyl ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, triacetin, and 1,6-hexanediol diacetate are particularly preferable.

The content of the high-boiling solvent in the organic solvent is preferably 0 to 50% by mass, more preferably 0.5 to 40% by mass, and particularly preferably 1 to 30% by mass. When the content ratio of the high boiling point solvent is not less than the lower limit, for example, foreign matter defects at the tip of the slit nozzle due to precipitation and solidification of a color material or the like tend to be avoided, and when the content ratio is not more than the upper limit, problems such as a tact failure in the reduced pressure drying process and pin hole marks in the pre-baking due to a decrease in the drying speed of the composition tend to be avoided.

In the photosensitive resin composition of the present invention, the content of the organic solvent is not particularly limited, but from the viewpoint of ease of application and viscosity stability, the total solid content in the photosensitive resin composition is preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, and particularly preferably 12% by mass or more, and further preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, and particularly preferably 20% by mass or less.

< other blending Components of photosensitive resin composition >

In addition to the above components, the photosensitive resin composition of the present invention may contain an adhesion improving agent, a coating property improving agent, a pigment derivative, a development improving agent, an ultraviolet absorber, an antioxidant, and the like as appropriate.

< adhesion improver >

The adhesive strength-improving agent may be contained to improve the adhesion to the substrate, 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. One kind of silane coupling agent may be used, or two or more kinds may be used in combination at any combination and ratio.

The photosensitive resin composition of the present invention may further contain an adhesion improving agent other than the silane coupling agent, and examples thereof include: phosphoric acid-based adhesion improving agents, other adhesion improving agents, and the like.

The phosphate adhesion improver is preferably a (meth) acryloyloxy group-containing phosphate, and among them, phosphate adhesion improvers represented by the following general formulae (g 1), (g 2) and (g 3) are preferable.

[ chemical formula 21]

In the above general formulae (g 1), (g 2) and (g 3), R ⁵¹ Each independently represents a hydrogen atom or a methyl group, l and l' are each independently an integer of 1 to 10, and m is each independently 1,2 or 3.

Other adhesion improving agents include TEGO ^* Add Bond LTH (Evonik). These phosphoric acid group-containing compounds and other sealing agents may be used singly or in combination of two or more.

The content ratio of the adhesion improver in the photosensitive resin composition is not particularly limited, and is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, particularly preferably 8% by mass or less, and most preferably 6% by mass or less in the entire solid content. When the amount is not less than the lower limit, adhesion to the substrate tends to be good, and when the amount is not more than the upper limit, residue during alkali development tends to be suppressed.

< agent for improving coatability >

In order to improve the coatability, a surfactant may be contained as a coating ability improver in the photosensitive resin composition of the present invention. Examples of the surfactant include: various surfactants such as anionic, cationic, nonionic and amphoteric surfactants. Among them, nonionic surfactants are preferably used from the viewpoint of low possibility of exerting adverse effects on various properties, and among them, fluorine-based or silicon-based surfactants are effective from the viewpoint of coatability.

Examples of such surfactants include: TSF4460 (manufactured by Momentive Performance Materials Co., ltd.), DFX-18 (manufactured by NEOS Co., ltd.), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie Co., ltd.), KP340 (manufactured by shin-Etsu Silicone Co., ltd.), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC Co., ltd.), SH7PA (manufactured by TORAY DOW CORNING Co., ltd.), DS-401 (manufactured by Dajin Co., ltd.), L-77 (manufactured by Japanese You Nika Co., ltd.), FC4430 (manufactured by 3M Japan) and the like. One kind of surfactant may be used, and two or more kinds may be used in combination in any combination and ratio.

The content 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 still more preferably 0.10% by mass or more, and is preferably 1.0% by mass or less, more preferably 0.7% by mass or less, still more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less, of the total solid content. When the content ratio of the surfactant is not less than the lower limit, the resist coating uniformity tends to be good, and when the content ratio is not more than the upper limit, the resist sensitivity tends to be lowered.

< pigment derivatives >

The photosensitive resin composition of the present invention may contain a pigment derivative for the purpose of improving dispersibility and storage stability. As the pigment derivative, there can be mentioned: azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, bisindanone

Azines, anthracenones, indanthrenes, perylenes, perinones, diketopyrrolopyrroles

Derivatives of oxazines and the like, among which phthalocyanines and quinophthalones are preferredAnd (4) class.

As substituents of the pigment derivative, there may be mentioned: sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, and the like, which may be bonded to the pigment skeleton directly or via an alkyl group, an aryl group, a heterocyclic group, and the like, and sulfonic acid groups are preferred. In addition, a plurality of these substituents may be substituted on one pigment skeleton. Specific examples of the pigment derivative include: sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, bis

Sulfonic acid derivatives of oxazines, and the like. These pigment derivatives may be used alone or in combination of two or more.

< method for producing photosensitive resin composition >

The photosensitive resin composition (hereinafter also referred to as "resist") of the present invention can be produced by a conventional method.

Generally, it is preferable to disperse the color material (d) in advance using a paint shaker, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. By the dispersion treatment, the (d) color material is finely pulverized, and thus the coating property of the resist is improved. In addition, when a black color material is used as the color material (d), it contributes to improvement of light shielding ability.

The dispersion treatment is preferably performed in a system in which (d) a color 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 used for the dispersion treatment and the composition obtained by the treatment are also referred to as "ink" or "pigment dispersion liquid"). In particular, the use of a polymeric dispersant as a dispersant is preferable because the thickening of the resulting ink and resist with time can be suppressed (excellent dispersion stability).

In the case where a liquid containing all the components to be blended with the photosensitive resin composition is subjected to dispersion treatment, the highly reactive components may be denatured by heat generated during the dispersion treatment. Therefore, the dispersion treatment is preferably performed in a system containing a polymeric dispersant.

When the color material (d) is dispersed by a sand mill, glass beads or zirconia beads having a diameter of about 0.1 to 8mm are preferably used. The temperature is usually 0 to 100 ℃ and preferably room temperature to 80 ℃ in terms of dispersion treatment conditions. The dispersion time is appropriately adjusted because there is a difference in suitable time depending on the composition of the liquid, the size of the dispersion treatment apparatus, and the like. The approximate criteria for dispersion are: the gloss of the ink is controlled so that the 20-degree specular gloss (JIS Z8741) of the resist falls within the range of 100 to 200. When the gloss of the resist is not less than the lower limit, the dispersion treatment becomes sufficient, coarse pigment (color material) particles are less likely to remain, and the developability, adhesion, resolution, and the like tend to become sufficient. When the gloss value is not more than the above upper limit, the pigment is likely to be prevented from being broken to generate a large amount of ultrafine particles, which in turn impairs dispersion stability.

Next, the ink obtained by the dispersion treatment is mixed with the other components contained in the resist to prepare a uniform solution. In the resist production process, since fine dust is often mixed into the liquid, it is preferable to perform a filtration process using a filter or the like on the obtained resist.

[ cured product ]

By curing the photosensitive resin composition of the present invention, a cured product can be obtained. The cured product obtained by curing the photosensitive resin composition can be preferably used as a member constituting a color filter such as a pixel, a black matrix, or a colored spacer.

[ Black matrix ]

Hereinafter, a black matrix using the photosensitive resin composition of the present invention will be described according to a method for producing the black matrix.

(1) Support body

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

In order to improve surface properties such as adhesiveness, the support may be subjected to corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, film formation treatment with various resins such as a silane coupling agent and a urethane resin, or the like, as necessary.

The thickness of the transparent substrate is usually in the range of 0.05 to 10mm, preferably 0.1 to 7 mm. When a thin film forming process is performed on various resins, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

(2) Black matrix

In order to form the black matrix of the present invention from the photosensitive resin composition of the present invention, a black matrix can be formed by applying the photosensitive resin composition of the present invention on a transparent substrate, drying the composition, placing a photomask on the coating film, performing image exposure and development through the photomask, and performing thermal curing or photo curing as necessary.

(3) Formation of black matrix

(3-1) coating of photosensitive resin composition

The photosensitive resin composition for black matrix can be applied to the transparent substrate by spin coating, wire bar (Wire bar) coating, flow coating, die coating, roll coating, spray coating, or the like. Among these, the use of the die coating method is preferable from the overall viewpoint of being able to greatly reduce the amount of the coating liquid used, being completely free from the influence of fogging or the like adhering during the spin coating, and being able to suppress the generation of foreign matter.

The thickness of the coating film is preferably in the range of usually 0.2 to 10 μm, more preferably 0.5 to 6 μm, and still more preferably 1 to 4 μm in terms of the film thickness after drying. When the amount is equal to or less than the above upper limit, pattern development tends to be facilitated, and gap adjustment in the step of forming a liquid crystal cell also tends to be facilitated. When the content is not less than the lower limit value, a desired color tends to be easily developed.

(3-2) drying of coating film

The coating film after coating the photosensitive resin composition on the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. The drying conditions may be appropriately selected depending on the kind of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected within a range of from 40 to 200 ℃ and from 15 seconds to 5 minutes, preferably from 50 to 130 ℃ and from 30 seconds to 3 minutes, depending on the kind of solvent component and the performance of the dryer used.

The higher the drying temperature, the more the adhesiveness of the coating film to the transparent substrate can be improved, but if the drying temperature is too high, the alkali-soluble resin may be decomposed to cause thermal polymerization and further cause development failure. The drying step of the coating film may be a reduced-pressure drying method in which drying is performed in a reduced-pressure chamber without raising the temperature.

(3-3) Exposure

The image exposure is performed by superimposing a negative mask pattern on a coating film of the photosensitive resin composition and irradiating light having a wavelength ranging from an ultraviolet region to a visible light region through the mask pattern. In this case, in order to prevent the decrease in sensitivity of the photopolymerizable layer due to oxygen, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable coating film and then exposed to light as necessary. The light source used for the image exposure is not particularly limited. Examples of the light source include: xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and the like. When light of a specific wavelength is irradiated and used, an optical filter may be used.

(3-4) development

The black matrix of the present invention can be produced as follows: the coating film formed from the photosensitive resin composition is image-exposed by the light source, and then developed using an organic solvent or an aqueous solution containing a surfactant and an alkali compound, thereby forming an image on a substrate. The aqueous solution may further comprise an organic solvent, a buffer, a complexing agent, a dye or a pigment.

As the basic compound, there may be mentioned: inorganic basic compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide, and organic basic compounds such as monoethanolamine, diethanolamine or triethanolamine, monomethylamine, dimethylamine or trimethylamine, monoethylamine, diethylamine or triethylamine, monoisopropylamine or diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These basic 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, anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfonates, and sulfosuccinates, and amphoteric surfactants such as alkylbetaines 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 treatment are not particularly limited, and the development temperature may be usually set in the range of 10 to 50 ℃, preferably 15 to 45 ℃, particularly preferably 20 to 40 ℃, and any of the immersion development method, the spray development method, the magnetic brush development method, the ultrasonic development method, and the like may be used as the development method.

(3-5) Heat curing treatment

The developed substrate is subjected to a heat curing treatment or a light curing treatment, and preferably subjected to a heat curing treatment. The conditions for the heat curing treatment in this case may be selected within a range of 100 to 280 ℃, preferably 150 to 250 ℃, and the time may be selected within a 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 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 image ]

A colored layer is produced by applying a photosensitive resin composition containing a coloring material of one of red, green and blue colors to a transparent substrate provided with a black matrix by the same process as in (3-1) to (3-5) above, drying the composition, laminating a photomask on the applied film, exposing and developing an image through the photomask, and forming a pixel image by heat curing or light curing as needed. This operation is performed for each of the photosensitive resin compositions of the three colors red, green, and blue, whereby a color filter image can be formed. Their order is not limited to the above.

[ colored spacer ]

The photosensitive resin composition of the present invention can be used as a black matrix and also as a resist for a colored spacer. When the spacer is used in a TFT-type LCD, the TFT as a switching element may malfunction due to light incident on the TFT, and a colored spacer is used to prevent this, and for example, japanese patent application laid-open No. 8-234212 describes that the spacer is made light-shielding. The colored spacer can be formed by the same method as the black matrix described above, except that a mask for the colored spacer is used.

(3-6) formation of transparent electrode

The color filter may be used as a part of a member of a color display, a liquid crystal display device, or the like by forming a transparent electrode such as ITO on an image in an original state, but a top coat layer such as polyamide or polyimide may be provided on the image as necessary for the purpose of improving surface smoothness and durability. In some applications such as an in-plane alignment driving method (IPS mode), a transparent electrode is not formed.

[ image display apparatus ]

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 for displaying images or videos, and examples thereof include a liquid crystal display device, an organic EL display, and the like, which will be described later.

[ liquid Crystal display device ]

The liquid crystal display device of the present invention is a display device having the cured product of the black matrix, the color filter pixel, the colored spacer, and the like of the present invention, and the order of formation, the position of formation, and the like of the color pixel and the black matrix are not particularly limited.

A liquid crystal display device is generally manufactured as follows: an alignment film is formed on a color filter, spacers are scattered on the alignment film, and then the liquid crystal cell is formed by bonding the alignment film to a counter substrate, and liquid crystal is injected into the formed liquid crystal cell to connect a line to a counter electrode, thereby completing a liquid crystal display device. The alignment film is preferably a resin film such as polyimide. The alignment film may be formed by a gravure printing method and/or a flexographic printing method, and the thickness of the alignment film may be several 10nm. After the alignment film is cured by thermal baking, the alignment film is processed into a surface state in which the liquid crystal can be adjusted in tilt by performing a surface treatment by irradiation with ultraviolet rays or a treatment with a rubbing cloth.

As the spacer, a spacer suitable for the size of the gap (gap) with the counter substrate can be used, and a spacer of 2 to 8 μm is generally preferable. It is also possible to form a Photosensitive Spacer (PS) of a transparent resin film on the color filter substrate by photolithography, and to effectively use the Photosensitive Spacer (PS) instead of the spacer. As the counter substrate, an array substrate is generally used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap between the counter substrate and the counter substrate varies depending on the application of the liquid crystal display device, but is usually selected within a range of 2 to 8 μm. After being bonded to the counter substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and/or heating, thereby sealing the periphery of the liquid crystal cell.

After the liquid crystal cell whose periphery is sealed is cut into a panel unit, the pressure in the vacuum chamber is reduced, the liquid crystal injection port is immersed in the liquid crystal, and then the pressure in the vacuum chamber is released, whereby the liquid crystal is injected into the liquid crystal cell. The degree of pressure reduction in the liquid crystal cell is usually 1X 10 ^-2 ～1×10 ^-7 Pa, preferably 1X 10 ^-3 ～1×10 ^-6 Pa. In addition, the liquid crystal cell is preferably heated at a temperature of usually 30 to 100 ℃ and more preferably 50 to 90 ℃ during the pressure reduction. The heating and holding time at the time of reduced pressure is usually set to a range of 10 to 60 minutes, and then immersed in the liquid crystal. The liquid crystal injection port is sealed by curing the UV curable resin to the liquid crystal cell in which the liquid crystal is injected, thereby completing the liquid crystal display device (panel).

The type of liquid crystal is not particularly limited, and may be any of conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, and may be any of lyotropic liquid crystals, thermotropic liquid crystals, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like are known, and any of them is possible.

[ organic EL display ]

The organic EL display of the present invention is manufactured using the color filter of the present invention.

When an organic EL display is manufactured using the color filter of the present invention, as shown in fig. 1, a color filter is first manufactured by forming a pattern formed of a photosensitive resin composition (i.e., pixels 20 and a resin black matrix (not shown) provided between adjacent pixels 20) on a transparent support substrate 10, and an organic light emitter 500 is laminated on the color filter through an organic protective layer 30 and an inorganic oxide film 40, thereby manufacturing an organic EL element 100. At least one of the pixels 20 and the resin black matrix is manufactured by using the photosensitive resin composition of the present invention. As a lamination method of the organic light-emitting body 500, there can be mentioned: a method of forming the transparent anode 50, the hole injection layer 51, the hole transport layer 52, the light emitting layer 53, the electron injection layer 54, and the cathode 55 on the color filter in a stepwise manner, a method of bonding the organic light emitting body 500 formed on another substrate to the inorganic oxide film 40, or the like. The organic EL element 100 thus fabricated can be used to fabricate an organic EL display by, for example, the method described in "organic EL display" (Ohmsha, ltd., 2004, 20/8/month, ren Jingshi, andda kyush, cuntian engien).

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

Examples

The present invention will be described in more detail below with reference to synthetic examples, examples and comparative examples, but the present invention is not limited to the following examples within the scope not exceeding the gist of the present invention.

< preparation of carbon Black ink >

A pigment, a dispersant, a dispersion aid (pigment derivative) and a solvent were blended according to the following compositions and methods to prepare a carbon black ink.

Specifically, first, the solid components of the pigment, the dispersant, and the dispersion aid, and the solvent are mixed so as to have the following amount ratios.

Pigment: RAVEN1060U (manufactured by Birror corporation, carbon black); 52.00 parts by mass

Dispersant: DISPERBYK-167 (basic urethane dispersant manufactured by BYK-Chemie Co., ltd.); 7.30 parts by mass (conversion of solid content)

Dispersing aid (pigment derivative): s12000 (phthalocyanine pigment derivative having an acid group, manufactured by Lubrizol corporation); 1.03 parts by mass

Solvent: propylene Glycol Monomethyl Ether Acetate (PGMEA); 112.04 parts by mass

These components were sufficiently stirred and mixed to obtain a dispersion.

Subsequently, the dispersion treatment was carried out for 6 hours at a temperature of 25 to 45 ℃ by a paint shaker. Zirconia beads having a diameter of 0.5mm were used as the beads, and the beads were added in a proportion of 180 parts by mass to 60 parts by mass of the dispersion. 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 mass%.

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

[ chemical formula 22]

50g of the epoxy compound (epoxy equivalent 264) having the above chemical structure, 13.65g of acrylic acid, 60.5g of 3-methoxybutyl acetate, 0.936g of triphenylphosphine, and 0.032g of p-methoxyphenol were put in a flask equipped with a thermometer, a stirrer, and a condenser, and reacted at 90 ℃ with stirring until the acid value became 5mgKOH/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 part by mass of Trimethylolpropane (TMP), 3.3 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 3.5 parts by mass of tetrahydrophthalic anhydride (THPA) were charged into a flask equipped with a thermometer, a stirrer, and a condenser, and the temperature was slowly raised to 105 ℃ while stirring to effect a reaction.

When the resin solution became transparent, the solution was diluted with 3-methoxybutyl acetate (MBA) to adjust the solid content to 50% by mass, thereby obtaining alkali-soluble resin (1) having an acid value of 115mgKOH/g and a weight average molecular weight (Mw) of 2,600 in terms of polystyrene as measured by GPC.

< synthetic example 2: synthesis of alkali-soluble resin (2) >

[ chemical formula 23]

7.3g of the epoxy compound having the above chemical structure (epoxy equivalent 240), 2.2g of acrylic acid, 6.4g of propylene glycol monomethyl ether acetate, 0.18g of tetraethylammonium chloride, and 0.007g of p-methoxyphenol were charged into a flask equipped with a thermometer, a stirrer, and a condenser, and reacted at 100 ℃ with stirring until the acid value became 5mgKOH/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 part by mass of Trimethylolpropane (TMP), 3.5 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), 0.06 part by mass of tetrahydrophthalic anhydride (THPA), and 14 parts by mass of Propylene Glycol Monomethyl Ether Acetate (PGMEA) were charged into a flask equipped with a thermometer, a stirrer, and a condenser, and the mixture was slowly heated to 105 ℃ while stirring to effect reaction, whereby an alkali-soluble resin (2) having a solid content of 40 mass%, an acid value of 100mgKOH/g, and a weight average molecular weight (Mw) in terms of polystyrene of 10,400 as measured by GPC was obtained.

< photopolymerization initiator (1) >

[ chemical formula 24]

A photopolymerization initiator (1) having the above chemical structure synthesized by the method described in International publication No. 2015/036910 was used. The photopolymerization initiator (1) thus obtained was dissolved in Propylene Glycol Monomethyl Ether Acetate (PGMEA) to prepare a 0.01 mass% solution, and an absorption spectrum was measured using a spectrophotometer U-3900H (Hitachi High-Tech Science, inc.), whereby the maximum absorption wavelength in the wavelength range of 320nm to 400nm was 331nm.

< photopolymerization initiator (2) >

[ chemical formula 25]

The photopolymerization initiator (2) having the above chemical structure synthesized by the method described in international publication No. 2008/078678 was used. The absorption spectrum was measured by the same method as that for the photopolymerization initiator (1), and as a result, the maximum absorption wavelength was 368nm.

< photopolymerization initiator (3) >

As the photopolymerization initiator (3), TR-PBG-314 (a compound having the following chemical structure) manufactured by Changzhou powerful electronic new material Co.

[ chemical formula 26]

The absorption spectrum was measured by the same method as that for the photopolymerization initiator (1), and as a result, the maximum absorption wavelength was 339nm.

< photopolymerization initiator (4) >

As the photopolymerization initiator (4), TR-PBG-358 (a compound having the following chemical structure) manufactured by Nippon powerful electronic New Material Co., ltd was used.

[ chemical formula 27]

The absorption spectrum was measured by the same method as in the photopolymerization initiator (1), and the maximum absorption wavelength was 344nm.

< photopolymerizable monomer >

LIGHT ACRYLATE PE-4A, available from Kyoeisha chemical Co., ltd., and KAYARAD DPCA-20, available from Nippon Chemicals, were prepared as photopolymerizable monomers.

[ chemical formula 28]

[ chemical formula 29]

< adhesion improving agent >

As the adhesion improving agent, KBM-5103, a product of shin-Etsu chemical Co., ltd., and KAYAMER PM-21, a product of Nippon chemical Co., ltd., a phosphoric acid-based adhesion improving agent were prepared.

[ chemical formula 30]

[ chemical formula 31]

The average value of a is approximately equal to 1.5, the average value of b is approximately equal to 1.5

< agent for improving coatability >

As the coating property improving agent, megafac F-554 (fluorine-containing group/lipophilic group-containing oligomer, nonionic surfactant) manufactured by DIC was prepared as a surfactant.

< example 1>

(preparation of Black resist 1)

Using the carbon black ink prepared in the above < preparation of carbon black ink >, the components were added so as to be in the proportions shown in table 1, and stirred and dissolved by a stirrer, to prepare a black resist 1. The total solid content in the black resist 1 was 15 mass%.

[ Table 1]

Note that the meanings of the abbreviations of the solvents in table 1 are as follows.

PGMEA: propylene glycol monomethyl ether acetate

MBA: acetic acid 3-methoxy butyl ester

EDGAC: diethylene glycol monoethyl ether acetate

< example 2>

(preparation of Black resist 2)

In the black resist 1 shown in table 1, a black resist 2 having a solid content of 15 mass% was prepared in the same manner as in the black resist 1 except that the total amount of the photopolymerization initiators was kept constant and the mixing ratio (mass%) of the photopolymerization initiators (1) and (2) was changed as shown in table 2.

[ Table 2]

Mixing ratio of photopolymerization initiator (%)

< example 3>

(preparation of Black resist 3)

In the black resist 1 shown in table 1, a black resist 3 having a solid content of 15 mass% was prepared in the same manner as in the black resist 1 except that the total amount of the photopolymerization initiators was kept constant and the mixing ratio (mass%) of the photopolymerization initiators (1) and (2) was changed as shown in table 2.

< comparative example 1>

(preparation of Black resist 4)

In the black resist 1 shown in table 1, a black resist 4 having a solid content of 15 mass% was prepared in the same manner as in the black resist 1 except that the total amount of the photopolymerization initiators was kept constant and the mixing ratio (mass%) of the photopolymerization initiators (1) and (2) was changed as shown in table 2.

< comparative example 2>

(preparation of Black resist 5)

In the black resist 1 shown in table 1, a black resist 5 having a solid content concentration of 15 mass% was prepared in the same manner as in the black resist 1 except that the total amount of the photopolymerization initiators was kept constant and the mixing ratio (mass%) of the photopolymerization initiators (1) and (2) was changed as shown in table 2.

< example 4>

(preparation of Black resist 6)

A black resist 6 having a solid content of 15 mass% was produced in the same manner as the black resist 2 except that the total amount of the photopolymerization initiators was kept constant in the black resist 2 of example 2 and the photopolymerization initiator (2) was changed to the photopolymerization initiator (3).

< example 5>

(preparation of Black resist 7)

A black resist 7 having a solid content of 15 mass% was produced in the same manner as the black resist 2 except that the total amount of the photopolymerization initiators was kept constant in the black resist 2 of example 2 and the photopolymerization initiator (2) was changed to the photopolymerization initiator (4).

(evaluation of Black resist)

(1) Fabrication of Black Matrix (BM) fine line patterns

The prepared black resists 1 to 7 were applied to a glass substrate by a spin coater, dried under reduced pressure, and then dried at 90 ℃ for 100 seconds by a hot plate. The coating conditions were adjusted so that the coating film thickness became about 1.2 μm. Next, the obtained dried coating film was exposed to 35mJ/cm using a high pressure mercury lamp (ADH-3000M-F-N, manufactured by ORC MANUFACTURING CORPORATION, no optical filter) using an exposure machine (EXF-2829-F-00, manufactured by ORC MANUFACTURING CORPORATION, inc.) to form a coating film ² Pattern exposure was performed through an exposure mask having linear openings with opening widths of 1 to 10 μm (1 μm span) and 15 μm (proximity alignment gap: 180 μm). Then, the resultant was dissolved at room temperature (23 ℃) for 2.2 times the time of dissolving the resultant in an alkali developing solution of KOH aqueous solution prepared with ultrapure water to 0.04 mass%After removing the unexposed portion by time-spray development (spray pressure: 0.1 MPa), the BM thin line pattern was formed by spray washing with ultrapure water (spray pressure: 0.1 MPa). The dissolution time is a time until the black resist film in the unexposed portion is dissolved and the substrate surface is observed during the development process, and the dissolution time of each black resist is in a range of 20 to 30 seconds.

(2) BM Fine line Pattern evaluation

The BM thin line pattern thus produced was observed with an optical microscope to confirm the state of formation of thin lines, and the thin line adhesion and sensitivity were evaluated, and the results are shown in table 3. The evaluation of the adhesion of the thin line and the sensitivity was performed according to the following criteria.

(evaluation of Fine wire adhesion)

In the alkali development, the BM thin line may corrode the bonding surface of the BM thin line/glass substrate to cause the embedding, and the thin line adhesion may be deteriorated. When the line pattern portion of 10 μm or less was observed with an optical microscope, and when the pattern of 8 μm or more was adhered and the pattern of 7 μm or less was peeled off, for example, the adhesion of the thin line was evaluated as 8 μm, and the line pattern portion was classified as described below (here, for example, the pattern in which the width of the opening of the exposure mask corresponded to 7 μm was described as a pattern of 7 μm). When the evaluation was "o", the fine line adhesion was good, when the evaluation was "very good", the evaluation was better, and when the evaluation was "x", the evaluation was poor.

Very good: thin lines of a pattern of 7 μm or more are closely adhered.

O: thin lines of a pattern of 8 μm or more are closely adhered (pattern peeling of 7 μm or less).

X: thin lines of a pattern of 9 μm or more were closely adhered (pattern peeling of 8 μm or less).

(evaluation of sensitivity)

In the case of a black resist, if the exposure sensitivity as a photosensitive resin composition is improved, the line width of the BM thin line to be formed tends to increase. The line width of the 15 μm line pattern was measured by an optical microscope, and the sensitivity was determined and classified as follows (for example, a pattern in which the width of the opening of the exposure mask corresponds to 15 μm is described as a 15 μm pattern). Note that, if the evaluation is "o", the sensitivity is evaluated to be good, and "x" is evaluated to be low.

O: 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.

[ Table 3]

As shown in table 3, the BM thin lines of examples 1 to 5 were excellent in both of the thin line adhesion and the sensitivity. The BM thin line of comparative example 1 showed high sensitivity, but on the other hand, the result of low adhesion of the thin line was obtained. The BM thin line of comparative example 2 showed good adhesion, but had low sensitivity.

In comparative example 1, since the surface of BM was strongly cured and the curing in the BM was insufficient, it is considered that the result of poor adhesion of the thin line to the thicker line width was obtained. In comparative example 2, since the curing on the BM surface was sparse and the curing inside the BM was strong, it is considered that the result of the fine line adhesion was good with respect to the fine line width. In examples 1 to 5, the curing balance between the surface and the inside of BM occurred well, and this is considered to be closely related to both the thin line adhesion and the high sensitivity.

Examples 1 to 5 have a large line width because of high sensitivity, but are advantageous from the following points of view.

The portion having a margin in sensitivity can reduce the amount of the photopolymerization initiator, and the reduced portion can be replaced with an alkali-soluble resin, a photopolymerizable monomer, or the like, thereby improving performance such as development resistance and substrate adhesion.

The portion where the exposure amount necessary for forming the target line width is decreased can increase the exposure speed, improving productivity. On the other hand, comparative example 1 also showed a high sensitivity, but because the curing inside BM was insufficient, further deterioration of the thin line adhesion occurred when the photopolymerization initiator was reduced in weight or the exposure amount was reduced.

The detailed mechanism of the effect of the present invention is not clear, but the following is presumed. That is, the photopolymerization initiator of diphenyl sulfide type is excellent in UV absorption ability in the vicinity of 330nm, but the benzofuran moiety of the condensed heterocycle included in the photopolymerization initiator (c 1) represented by the general formula (I) promotes adsorption of the photopolymerization initiator (c 1) to the surface of the color material particle by increasing the interaction force with the color material, particularly carbon black. The light absorbed by the color material does not contribute to polymerization and becomes a factor that reduces the exposure sensitivity, but the light absorptance with respect to the photopolymerization initiator is increased by covering the surface of the color material with the photopolymerization initiator. Further, adsorption of the photopolymerization initiator to the color material relatively lowers the photopolymerization initiator concentration in the resin component, and thus the light transmittance to the deep part is improved. This improves the internal curability of the resist film, contributing to the improvement of the adhesion of the thin line.

However, when only the photopolymerization initiator (c 1) is used, sufficient sensitivity cannot be obtained by using only a part of the UV wavelength region of the exposure light source on the lower wavelength side, and therefore, by using the photopolymerization initiator (c 2) having a maximum absorption wavelength in the long wavelength region in combination, sensitivity, particularly surface sensitivity can be improved. Since there is a difference in maximum absorption wavelength between the photopolymerization initiator (c 1) and the photopolymerization initiator (c 2), the influence of the combined use on the internal curability can be suppressed. It is considered that both the surface sensitivity and the internal curing can be improved thereby.

As described above, it is found that the use of the photosensitive resin composition of the present invention can provide a photosensitive resin composition having high sensitivity and excellent fine line adhesion performance.

While the present invention has been described in detail with reference to the specific embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. The present application was made based on Japanese patent application laid-open at 2016 (Japanese patent application 2016-181932), the entire contents of which are incorporated herein by reference.

Claims

1. A photosensitive resin composition comprising:

(a) Alkali soluble resin,

(b) A photopolymerizable monomer,

(c) Photopolymerization initiator, and

(d) The color material is selected from a group of color materials,

wherein the photopolymerization initiator (c) comprises a photopolymerization initiator (c 1) represented by the general formula (I) below and a photopolymerization initiator (c 2) having a maximum absorption wavelength of 334nm or more in a wavelength range of 320nm to 400nm,

in the formula (I), R ¹ Represents an optionally substituted alkyl group or an optionally substituted aromatic ring group,

R ² represents an optionally substituted alkyl group or an optionally substituted aromatic ring group,

k represents a number of 0 or 1,

R ³ ～R ⁶ each independently represents an arbitrary 1-valent substituent,

2. The photosensitive resin composition according to claim 1, wherein a content ratio of the color material (d) to the total solid content is 20% by mass or more.

3. The photosensitive resin composition according to claim 2, wherein a content ratio of the color material (d) to the total solid content is 30% by mass or more.

4. The photosensitive resin composition according to claim 2, wherein a content ratio of the color material (d) to the total solid content is 60% by mass or less.

5. The photosensitive resin composition according to claim 3, wherein a content ratio of the color material (d) to the total solid content is 60% by mass or less.

6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the photopolymerization initiator (c 2) is a photopolymerization initiator having a fluorene skeleton or a carbazole skeleton.

7. The photosensitive resin composition according to claim 6, wherein the photopolymerization initiator (c 2) is a photopolymerization initiator represented by the following general formula (II),

in the formula (II), R ⁷ Represents an optionally substituted alkyl group or an optionally substituted aromatic ring group,

R ⁸ represents an alkyl group optionally having a substituent or an aromatic ring group optionally having a substituent,

p represents a number of 0 or 1,

R ⁹ represents an optional substituent having a valence of 1, q represents an integer of 0 to 3,

x represents-N (R) ¹⁰ ) -or-C (R) ¹¹ )(R ¹² )-，

R ¹⁰ ～R ¹² Each independently represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aromatic ring group, R ¹¹ And R ¹² Optionally bonded to each other to form a ring.

8. The photosensitive resin composition according to any one of claims 1 to 5, wherein a content ratio of the photopolymerization initiator (c) to the total solid content is 2% by mass or more.

9. The photosensitive resin composition according to any one of claims 1 to 5, wherein a content ratio of the photopolymerization initiator (c 1) in the photopolymerization initiator (c) is 1% by mass or more.

10. The photosensitive resin composition according to any one of claims 1 to 5, wherein the coloring material (d) is carbon black.

11. The photosensitive resin composition according to any one of claims 1 to 5, wherein the alkali-soluble resin (a) contains an epoxy (meth) acrylate resin having a carboxyl group.

12. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 11.

13. An image display device comprising the cured product according to claim 12.