JP2016024319A - Photosensitive resin composition, cured product obtained by curing the same, black matrix and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that has excellent adhesion to a substrate at room temperature and at high temperature and high humidity in the case of high colorant concentration and miniaturization.SOLUTION: A photosensitive resin composition comprises an alkali-soluble resin (a), a photopolymerizable monomer (b), a photopolymerization initiator (c), a colorant (d), a dispersant (e) and an organic silicon compound (f). The organic silicon compound (f) comprises at least an organic silicon compound (f-1) having a structure represented by general formula (1).SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition, a cured product obtained by curing the photosensitive resin composition, a black matrix, and an image display device. In detail, it is related with the photosensitive resin composition excellent in the adhesiveness to a board | substrate especially, and its use.

  An image display device such as a liquid crystal display (LCD) typified by a notebook computer or a liquid crystal television needs a color filter having a pixel and a black matrix (hereinafter sometimes abbreviated as BM), a spacer, and the like. A color filter is also required for colorization of a solid-state imaging device typified by a charge coupled device (CCD, CMOS) used as an input device for a digital camera, a color copier, or the like.

  In the pixel forming method by the pigment dispersion method generally used at present, first, a photosensitive resin composition is applied onto a substrate such as a glass substrate or a wafer, and then prebaked to form a film, and then a predetermined mask. The irradiated portion is irradiated with an ultraviolet ray, the irradiated portion is cured, the unirradiated portion is removed by an alkali development treatment, and a heat treatment is performed at a temperature of 200 ° C. or higher to obtain a colored cured film (colored pixel). This method is based on the principle that a photopolymerization initiator generates an active radical by ultraviolet irradiation, which attacks a photopolymerizable compound and induces a polymerization reaction. That is, active radicals are present and polymerization is initiated for the first time.

  The photosensitive resin compositions used in these image display devices and solid-state imaging devices are increasingly required to be finer and thinner as the devices themselves become lighter, thinner, and thinner, and the resin component in the composition is reduced. It is also considered to omit organic undercoat films. In addition, a high light shielding degree and a high color density reproduction are required, and the color material density is becoming higher. For this reason, the sensitivity is lowered and the adhesion to the substrate is reduced accordingly, and improvement by various methods such as a photopolymerization initiator has been attempted.

  Since the coexisting colorant also absorbs ultraviolet rays when irradiated with ultraviolet rays, if the content of the colorant is increased, the generation of active radicals is hindered, curing becomes insufficient, and the adhesion to the substrate is reduced. On the other hand, when the amount of the photopolymerization initiator is increased in order to increase the generation of active radicals, the ultraviolet rays are absorbed by the initiator in the surface layer portion, the ultraviolet rays do not reach the inside, and the improvement of insufficient curing is not sufficient.

  Further, in recent years, in order to save energy, the market has been studying to increase the brightness by further narrowing the line width of BM. In addition, in order to reduce the manufacturing process at the time of producing a liquid crystal panel, a conventional frame portion is made of BM, and a sealing agent is applied thereon, and a TFT substrate is bonded to the other. In addition, the substrate adhesion of BM is required at the time of transportation to an increasing overseas market or in a high temperature and high humidity environment.

  While the demand for substrate adhesion at room temperature, further high temperature and high humidity is increasing in the situation of BM miniaturization and thinning, as a method for improving the adhesion of pixels and BM to the substrate, A method of adding an adhesion improver to the photosensitive resin composition has been studied. For example, Patent Document 1 discloses that adhesion of BM is improved by using a silane coupling agent such as epoxy, (meth) acryl, vinyl, or the like. It is described to improve. Patent Document 2 describes that the development adhesion is improved by using a secondary, tertiary amine, ketimine, or isocyanate silane coupling agent.

JP-A-10-133370 JP 2008-129463 A

As a result of intensive studies by the present inventors, the adhesion improvers described in Patent Documents 1 and 2 are used at room temperature and high temperature and high humidity in the case of a high colorant concentration or high fineness. It was found that the substrate adhesion was not practically sufficient.
Accordingly, an object of the present invention is to provide a photosensitive resin composition having good substrate adhesion at room temperature and under high temperature and high humidity in the case of a high colorant concentration or in the case of high miniaturization.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by incorporating a specific organosilicon compound into the photosensitive resin composition.
That is, the gist of the present invention is as follows.

[1] Photosensitive resin composition containing alkali-soluble resin (a), photopolymerizable monomer (b), photopolymerization initiator (c), colorant (d), dispersant (e) and organosilicon compound (f) A thing,
A photosensitive resin composition, wherein the organosilicon compound (f) contains at least an organosilicon compound (f-1) having a structure represented by the following general formula (1).

(In the above formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ^Ra is a group represented by the following formula (1-1). * Is a bond.)

（上記式中、Ｒ²及びＲ³はそれぞれ独立に炭素数１〜８のアルキレン基であり、Ｒ⁴は水素原子又はメチル基である。＊はＳｉ原子との結合手である。）
［２］ 有機ケイ素化合物（ｆ−１）が、下記一般式（２）で表される有機ケイ素化合物を含むことを特徴とする、［１］に記載の感光性樹脂組成物。

(In the above formula, R ² and R ³ are each independently an alkylene group having 1 to 8 carbon atoms, R ⁴ is a hydrogen atom or a methyl group, and * is a bond with a Si atom.)
[2] The photosensitive resin composition according to [1], wherein the organosilicon compound (f-1) includes an organosilicon compound represented by the following general formula (2).

(In the above formula, R ¹ and R ^a have the same meaning as in the general formula (1). R ¹ contained in the formula may be the same or different.)
[3] The photosensitive resin composition according to [1] or [2], wherein the organosilicon compound (f-1) includes an organosilicon compound represented by the following general formula (3).

(In the above formula, R ¹ and R ^a have the same meaning as in the general formula (1). N represents an integer of 2 to 10. R ¹ and R ^a contained in the formula are the same as each other. Or different.)
[4] The photopolymerizable monomer (b) contains a compound represented by at least one of the following general formulas (b1) to (b4), according to any one of [1] to [3] Photosensitive resin composition.

(In the above formula, R ^b is a group represented by the following formula (b5), and R ⁹ is an alkylene group having 1 to 10 carbon atoms, an arylene alkylene group having 7 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms. .)

(In the above formula, R ⁶ represents an alkylene group that may have 2 to 6 carbon atoms in the main chain, R ⁷ represents a hydrogen atom or a methyl group, and m represents an integer of 0 to 3. When m is 2 or 3, a plurality of R ⁶ may be the same or different.)
[5] The photosensitive resin composition according to any one of [1] to [4], wherein the photopolymerization initiator (c) is an oxime ester.
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the color material (d) is a black color material.
[7] The photosensitive resin composition according to any one of [1] to [6], wherein the content of the coloring material (d) is 40% by mass or more based on the total solid content.
[8] The photosensitive resin composition according to any one of [1] to [7], wherein the dispersant (e) is a polymer dispersant having a basic functional group.
[9] The photosensitive resin composition according to any one of [1] to [8], wherein the alkali-soluble resin (a) contains an ethylenically unsaturated group.
[10] The photosensitive resin composition according to [9], wherein the alkali-soluble resin (a) contains an epoxy (meth) acrylate resin having a carboxyl group.
[11] The epoxy (meth) acrylate resin having a carboxyl group contains the following epoxy (meth) acrylate resin (A1-1) and / or the following epoxy (meth) acrylate resin (A1-2). The photosensitive resin composition according to [10].
Epoxy (meth) acrylate resin (A1-1): An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to the epoxy resin, and a polybasic acid and Epoxy (meth) acrylate resin obtained by reacting an anhydride thereof / Epoxy (meth) acrylate resin (A1-2): α, β-unsaturated monocarboxylic acid or α having a carboxyl group on the epoxy resin , Β-unsaturated monocarboxylic acid ester, and epoxy (meth) acrylate resin obtained by reacting polyhydric alcohol with polybasic acid and / or anhydride thereof

[12] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [11].
[13] A black matrix comprising the cured product according to [12].
[14] The black matrix according to [13], wherein the optical density per 1 μm film thickness is 4.0 or more.
[15] An image display device produced using the black matrix according to [13] or [14].

  ADVANTAGE OF THE INVENTION According to this invention, in the case of a high color material density | concentration and the case of high refinement | miniaturization, the photosensitive resin composition which becomes favorable the board | substrate adhesiveness under room temperature and high temperature high humidity can be provided.

It is a cross-sectional schematic diagram which shows an example of the organic EL element provided with the color filter of this invention.

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

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

[Photosensitive resin composition]
The photosensitive resin composition of the present invention comprises an alkali-soluble resin (a), a photopolymerizable monomer (b), a photopolymerization initiator (c), a colorant (d), a dispersant (e), and an organosilicon compound (f ), Wherein the organosilicon compound (f) contains an organosilicon compound (f-1) having a structure represented by the following formula (1).

In the above formula, R ¹ is hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ^a is a group represented by the following formula (1-1). * Is a bond.

In the above formula, R ² and R ³ are each independently an alkylene group having 1 to 8 carbon atoms, and R ⁴ is a hydrogen atom or a methyl group. * Is a bond with a Si atom.

The photosensitive resin composition of the present invention may further contain a dispersion aid and a polyfunctional thiol compound, and if necessary, other adhesion improvers, coatability improvers, development improvers, ultraviolet absorptions. Other compounding components such as an agent, an antioxidant and a surfactant may be contained, and each compounding component is usually used in a state dissolved or dispersed in an organic solvent.
One of the characteristics of the present invention is that the photosensitive resin composition contains the organosilicon compound (f). First, the organosilicon compound (f) will be described.

<Organic silicon compound (f)>
The organosilicon compound (f) in the present invention contains at least an organosilicon compound (f-1) having a structure represented by the following formula (1).

In the above formula, R ¹ is hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ^a is a group represented by the following formula (1-1). * Is a bond.

In the above formula, R ² and R ³ are each independently an alkylene group having 1 to 8 carbon atoms, and R ⁴ is a hydrogen atom or a methyl group. * Is a bond with a Si atom.

The alkyl group having 1 to 8 carbon atoms in R ¹ of the general formula (1) may be linear, branched or cyclic. From the viewpoint of ease of handling and reactivity, the number of carbon atoms is preferably 4 or less, and more preferably 3 or less.
Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopentyl group, and a cyclohexyl group. Among these, from the viewpoint of reactivity, a methyl group, an ethyl group, a propyl group, or a butyl group is preferable, and a methyl group or an ethyl group is more preferable.

The alkylene group having 1 to 8 carbon atoms in R ² and R ³ of the general formula (1-1) may be linear, branched, or cyclic. From the viewpoint of ease of handling and reactivity, the number of carbon atoms is usually 1 or more, preferably 2 or more, preferably 6 or less, and more preferably 4 or less.
For example, methylene group, ethylene group, 1,3-propylene group, 1,2-propylene group, 1,4-butylene group, 1,2-butylene group, 1,5-pentylene group, 1,6-hexylene group, Examples thereof include a cyclohexylene group and a methylenecyclohexylene group. Among these, methylene group, ethylene group, 1,3-propylene group, 1,2-propylene group, 1,4-butylene group, or 1,2-butylene group is preferable from the viewpoint of easy handling and reactivity. An ethylene group, a 1,3-propylene group, or a 1,2-propylene group is more preferable.

  Examples of the organosilicon compound having a structure represented by the general formula (1) include a monomer of an organosilicon compound represented by the following general formula (2).

In said formula, R < ¹ > and ^Ra is synonymous with the said General formula (1). A plurality of R ¹ contained in the formula may be the same or different.

  Although the monomer of the general formula (2) itself has the structure of the general formula (1), an oligomer of the monomers and an oligomer of the monomer and an organosilicon compound having another structure are also included. And having the structure of the general formula (1).

Examples of the organosilicon compound (f-1) having the structure represented by the general formula (1) include the following four embodiments.
Embodiment 1: An organosilicon compound containing the monomer of the general formula (2).
-Embodiment 2: The organosilicon compound containing the oligomer of the monomers of the said General formula (2).
-Embodiment 3: The organosilicon compound containing the oligomer of the monomer of the said General formula (2), and monomers other than the said General formula (2).
Embodiment 4: An organosilicon compound containing an oligomer of the oligomer of Embodiment 2 and a monomer other than the general formula (2).

<Organic silicon compound of Embodiment 1>
The organosilicon compound (f-1) of Embodiment 1 is an organosilicon compound containing a monomer represented by the following general formula (2).

In said formula, R < ¹ > and ^Ra is synonymous with the said General formula (1). A plurality of R ¹ contained in the formula may be the same or different.

  The monomer represented by the general formula (2) includes an organosilane compound having an isocyanate group represented by the following general formula (2-1) and a hydroxyl group represented by the following general formula (2-2). It can be obtained by a known method in which a (meth) acryloyloxy compound having a urethanization reaction in the presence of a catalyst.

(R ¹ O) ₃ Si—R ² —N═C═O (2-1)
(In the above formula, R ¹ and R ² have the same meanings as the general formulas (1) and (1-1).)
HO—R ³ —O—CO—CR ⁴ ═CH ₂ (2-2)
(In the above formula, R ³ and R ⁴ have the same meaning as in the general formula (1-1).)

  Examples of the catalyst in this reaction include organotin compounds such as dibutyltin malate, tributyltin acetate, dimethyltin dichloride, dibutyltin diacetate, and dibutyltin dilaurate; N-methylmorpholine, triethylamine, N-methylpiperidine, N, N-dimethyl Tertiary amines such as cyclohexylamine and pyridine are useful, and the addition amount thereof is 0.001 to 1% by mass, particularly 0.01 to 0. 0% with respect to the silane compound of the general formula (2-1). 1% by mass is preferred. 0-50 degreeC is preferable and, as for reaction temperature, 20-40 degreeC is more preferable. The reaction time can be appropriately selected from 1 to 24 hours. The above reaction may usually be performed without a solvent, but an organic solvent such as hexane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran, or acetonitrile may be used as necessary.

  Specific examples of the monomer represented by the general formula (2) include the following, but are not particularly limited as long as they satisfy the general formula (2).

However, the monomer of Embodiment 1 may be a mixture of plural types of monomers satisfying the general formula (2). In addition, the organosilicon compound of Embodiment 1 is preferably one containing a monomer as a main component, but includes one that is partially oligomerized due to the influence of moisture or heat due to aging during storage. May be. The organosilicon compound (f) of Embodiment 1 may contain a monomer having a structure other than the general formula (2) as long as the effect of the present application is not affected.
In Embodiment 1, the content ratio of the monomer represented by the general formula (2) with respect to the organosilicon compound (f-1) is preferably 10 mol% or more, more preferably 50 mol% or more, and still more preferably. It is 65 mol% or more, particularly preferably 80 mol% or more, and usually 100 mol% or less. By setting it to the lower limit value or more, there is a tendency that adhesion with the substrate can be improved.
Moreover, the content ratio of the monomer represented by the general formula (2) with respect to the organosilicon compound (f) is preferably 10 mol% or more, more preferably 50 mol% or more, still more preferably 65 mol% or more, Especially preferably, it is 80 mol% or more, and usually 100 mol% or less. By setting it to the lower limit value or more, there is a tendency that adhesion with the substrate can be improved.

<Organic silicon compound of Embodiment 2>
The organosilicon compound (f-1) of Embodiment 2 is an organosilicon compound containing an oligomer represented by the following general formula (3).

In said formula, R < ¹ > and ^Ra is synonymous with the said General formula (1). N represents an integer of 2 to 10. A plurality of R ¹ and R ^a included in the formula may be the same or different.

  In order to obtain good adhesion to the substrate, n is preferably an integer of 2 to 8, and more preferably an integer of 2 to 5. The oligomer represented by the general formula (3) is obtained by oligomerizing the monomer represented by the general formula (2) described in Embodiment 1 by a general method such as hydrolysis and heating. . Details will be described later.

The organosilicon compound (f-1) in Embodiment 2 may include not only the oligomer represented by the general formula (3) but also a monomer represented by the general formula (2). Moreover, the organosilicon non-compound (f) in Embodiment 2 is a range which does not affect the effect of this invention for monomers other than the said General formula (2), and oligomers other than the said General formula (3). It may be included.
The case where the organosilicon compound (f-1) in Embodiment 2 contains both the monomer represented by the general formula (2) and the oligomer represented by the general formula (3) is preferable. The reason for this is that with monomers alone, volatilization may be reduced by high-temperature treatment during color filter creation, but with oligomers alone, oligomers are further hydrolyzed and polymerized by high-temperature treatment, resulting in a large molecular weight. This is because it tends to remain as a residue on the substrate during alkali development.

  Specific examples of the oligomer represented by the general formula (3) include the following, but are not particularly limited as long as the structure represented by the general formula (3) is satisfied.

  The organosilicon compound (f) of Embodiment 2 may contain other monomers and oligomers as long as they do not affect the adhesion effect.

In Embodiment 2, the content ratio of the oligomer represented by the general formula (3) with respect to the organosilicon compound (f-1) is preferably 10 mol% or more, more preferably 50 mol% or more, and further preferably 65 mol. % Or more, particularly preferably 80 mol% or more, and usually 100 mol% or less. By setting it to the lower limit value or more, there is a tendency that adhesion with the substrate can be improved.
The content ratio of the oligomer represented by the general formula (3) with respect to the organosilicon compound (f) is preferably 10 mol% or more, more preferably 50 mol% or more, still more preferably 65 mol% or more, particularly preferably. Is 80 mol% or more and usually 100 mol% or less. By setting it to the lower limit value or more, there is a tendency that adhesion with the substrate can be improved.

Further, when the organosilicon compound (f-1) includes both the monomer represented by the general formula (2) and the oligomer represented by the general formula (3), the organosilicon compound (f-1) The total content of the monomer represented by the general formula (2) and the oligomer represented by the general formula (3) is preferably 10 mol% or more, more preferably 50 mol% or more, and still more preferably. Is 65 mol% or more, particularly preferably 80 mol% or more, and usually 100 mol% or less. By setting it to the lower limit value or more, there is a tendency that adhesion with the substrate can be improved.
The ratio of the mass of the oligomer represented by the general formula (3) to the monomer represented by the general formula (2) is the mass of the monomer represented by the general formula (2). : The mass content of the oligomer represented by the general formula (3) is preferably in the range of 0.1: 99.9 to 99.9: 0.1. There exists a tendency which can make board | substrate adhesiveness favorable by setting it as the said range.

  The weight average molecular weight of the oligomer represented by the general formula (3) is preferably 10,000 or less, more preferably 6500 or less, further preferably 3500 or less, and preferably 2000 or less. Particularly preferred. By setting it to the upper limit or less, there is a tendency that the residue on the substrate at the time of alkali development can be made favorable.

  Although it does not specifically limit about the method of obtaining the oligomer represented by the said General formula (3), For example, it is obtained by making the monomer represented by the said General formula (2) hydrolyze. Specifically, the monomer is put into a solvent that can be easily removed by distillation later, such as alcohol or propylene glycol methyl ether acetate, and a small amount of acid such as oxalic acid is added as a catalyst, or ionic water is added, An oligomer is obtained by heating at 50 to 150 ° C. for 1 to 12 hours. These hydrolysis reactions are carried out by a generally known method. For example, the hydrolysis reaction is carried out by the method described in paragraphs [0098] to [0099] of JP 2012-27480 A or the method described in the synthesis example. Can be obtained.

<Organic silicon compound of Embodiment 3>
The organosilicon compound (f-1) of Embodiment 3 is an oligomer of a monomer represented by the general formula (2) and a monomer other than the general formula (2) (hereinafter referred to as “copolymer oligomer”). It is an organosilicon compound that may be abbreviated.

  In the organosilicon compound (f-1) of Embodiment 3, for example, the monomer represented by the general formula (2) and the monomer other than the general formula (2) are described in Embodiment 2. It can be obtained by a method of oligomerization by such a hydrolysis reaction.

  In addition to the structure of the general formula (1) derived from the monomer represented by the general formula (2), by introducing a structure derived from a monomer other than the general formula (2), photosensitivity is obtained. The interaction with the alkali-soluble resin, the photopolymerizable monomer, the photopolymerization initiator, the colorant, the dispersant, and the like in the water-soluble resin composition can be adjusted, and the effects resulting from the structure of the general formula (1) In addition, there is a tendency that further improvement in adhesion, sensitivity, and good pattern shape formation are obtained. In particular, the introduction of a structure derived from a monomer having a hydroxyl group or a carboxyl group with good alkali developability tends to improve the alkali development residue.

  Specific examples of the monomer other than the general formula (2) include the following vinyl group, epoxy group, styryl group, methacryl group, acrylic group, primary, secondary, tertiary amino group, and ureido group. , Mercapto groups, isocyanate groups and the like.

Other than that, a monomer having an epoxy group, oxetanyl group, episulfide group, vinyl group, allyl group, (meth) acryloyl group, carboxyl group, hydroxyl group, mercapto group, isocyanate group, amino group, ureido group, styryl group Specific examples of the body are described in paragraphs [0082] to [0095] of JP 2012-27480 A, and these can also be used as the monomer of Embodiment 3.
In addition, the monomers described in the paragraphs [0096] to [0097] of the publication may also be used as the monomer of Embodiment 3 as long as the effects of the present invention are not affected.
In addition, monomers other than those described above can also be used as the monomer of Embodiment 3 as long as the effects of the present invention are not affected.

  Moreover, the organosilicon compound (f-1) of Embodiment 3 may contain an oligomer represented by the general formula (3), and a monomer represented by the general formula (2). May be included. Furthermore, the organosilicon compound (f) may contain other silane monomers to the extent that the adhesion effect of the present invention is not affected.

In Embodiment 3, the content ratio of the copolymer oligomer to the organosilicon compound (f-1) is preferably 10 mol% or more, more preferably 50 mol% or more, still more preferably 65 mol% or more, and particularly preferably 80. It is at least mol% and usually at most 100 mol%. By setting it to the lower limit value or more, there is a tendency that adhesion with the substrate can be improved.
The content of the copolymer oligomer with respect to the organosilicon compound (f) is preferably 5 mol% or more, more preferably 30 mol% or more, still more preferably 50 mol% or more, particularly preferably 65 mol% or more. Usually, it is 100 mol% or less. By setting it to the lower limit value or more, there is a tendency that adhesion with the substrate can be improved.

  The weight average molecular weight of the copolymer oligomer of Embodiment 3 is preferably 30000 or less, more preferably 10,000 or less, and even more preferably 5000 or less. By setting it to the upper limit value or less, there is a tendency that residues can be suppressed from remaining on the substrate during alkali development.

<Organic Silicon Compound of Embodiment 4>
The organosilicon compound (f-1) of Embodiment 4 is abbreviated as an oligomer (hereinafter, “block oligomer”) of an oligomer represented by the general formula (3) and a monomer other than the general formula (2). In some cases).

  The organosilicon compound (f-1) of the fourth embodiment includes, for example, an oligomer represented by the general formula (3) and a monomer other than the general formula (2) as described in the second embodiment. It is obtained by a method of oligomerization by hydrolysis reaction.

  In addition to the structure of the general formula (1) derived from the oligomer represented by the general formula (3), a structure derived from a monomer other than the general formula (2) is introduced, so that Embodiment 3 As described in the above, there is a tendency that further improvement in adhesion, improvement in sensitivity, improvement in good pattern shape formation, and the like are obtained. In particular, the introduction of a structure derived from a monomer having a hydroxyl group or a carboxyl group with good alkali developability tends to improve the alkali development residue.

  As the monomer other than the general formula (2), the monomers described in Embodiment 3 can be applied.

  In addition, the organosilicon compound (f-1) of Embodiment 4 may include the copolymer oligomer, may include the oligomer represented by the general formula (3), and may include the general formula. The monomer represented by (2) may be included. Furthermore, the organosilicon compound (f) may contain other silane monomers and the like to such an extent that the adhesion effect of the present invention is not affected.

In Embodiment 4, the content ratio of the block oligomer with respect to the organosilicon compound (f-1) is preferably 10 mol% or more, more preferably 50 mol% or more, further preferably 65 mol% or more, particularly preferably 80 mol. % Or more and usually 100 mol% or less. By setting it to the lower limit value or more, there is a tendency that adhesion with the substrate can be improved.
The content of the block oligomer with respect to the organosilicon compound (f) is preferably 5 mol% or more, more preferably 30 mol% or more, further preferably 50 mol% or more, particularly preferably 65 mol% or more, and usually 100 mol% or less. By setting it to the lower limit value or more, there is a tendency that adhesion with the substrate can be improved.

  Moreover, the weight average molecular weight of the block oligomer of Embodiment 4 is preferably 20000 or less, more preferably 8000 or less, and further preferably 4000 or less. By setting it to the upper limit value or less, there is a tendency that residues can be suppressed from remaining on the substrate during alkali development.

  Moreover, in Embodiments 1-4, it is preferable that the content rate of the organosilicon compound (f) in the photosensitive resin composition is 0.01 mass% or more in a total solid, and is 0.1 mass% or more. More preferably, it is preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less. . When the amount is not less than the lower limit, there is a tendency that adhesion to the substrate can be improved, and when the amount is not more than the upper limit, there is a tendency that it is possible to suppress residue from remaining on the substrate during alkali development.

  As mentioned above, although Embodiment 1-4 was demonstrated in detail, as an organosilicon compound (f-1), the organosilicon compound (f-1) of Embodiment 1 or Embodiment 2 is preferable, and especially the said General formula (3) It is preferable that it is a mixture of the oligomer represented by this, and the monomer represented by the said General formula (2).

<(1) Multifunctionalization of ethylenically unsaturated group of formula structure>
The ethylenically unsaturated group in the general formula (1-1) can be polyfunctionalized as follows. As a method for obtaining a polyfunctionalized organosilicon compound (f-1), for example, a method using a monomer in which the ethylenically unsaturated group is polyfunctionalized in the monomer of the general formula (2) is used. It is done. Specifically, it can be obtained by the same method as in Embodiment 1 using compounds of the following general formula (2-1) and the following general formula (2-3).

(R ¹ O) ₃ Si—R ² —N═C═O (2-1)
(In the above formula, R ¹ and R ² have the same meanings as the general formulas (1) and (1-1).)
X—Y— (O—CO—CR ⁴ ═CH ₂ ) _m (2-3)
(In the above formula, X represents a hydroxyl group, a thiol group, a primary amino group, or a secondary amino group, Y represents an m + 1 valent organic group, and R ⁴ has the same meaning as in the general formula (1-1). M is an integer from 2 to 6).

  Specific examples of the compound of the general formula (2-3) include pentaerythritol triacrylate and dipentaerythritol pentaacrylate. In addition, any compound that satisfies the general formula (2-3) can be used.

  As another method of polyfunctionalization, for example, in the monomer of the general formula (2), active hydrogen on nitrogen of the urethane bond is dechlorinated with a compound having an ethylenically unsaturated group and an alkyl chloride group. Examples include a method of performing a hydrogen reaction. Specifically, NH in the urethane bond may be further added with an unsaturated group by adding 4-vinylbenzyl chloride or the like. Various other known general methods can be applied.

<Other organosilicon compounds>
As described above, the organosilicon compound (f) contains at least the organosilicon compound (f-1) having the structure represented by the general formula (1), but represented by the general formula (1). Other organosilicon compounds that do not have the structure described above may be included. For example, a monomer represented by the following formula (4) or (5), which is similar to the general formula (2), may be mentioned.

In said formula, R < ¹ > -R < ⁴ > is synonymous with the said Formula (2). R ^α represents a —S— group or a —NH— group.

In said formula, R < ¹ > -R < ⁴ > is synonymous with the said Formula (2). R ^β represents an —O— group, an —S— group, or an —NH— group.

The silane monomer represented by the general formula (4) includes a silane compound containing an isocyanate represented by the following general formula (4-1), and the following general formula (4-2) or (4-3). (Meth) acryloyloxy compound can be synthesized by a thiourethane reaction or a urea reaction in the presence of a catalyst as in the known method described in the first embodiment.
(R ¹ O) ₃ Si—R ² —N═C═O (4-1)
(In the above formula, R ¹ and R ² have the same meaning as in the general formula (4).)
^{HS-R 3 -O-CO-} CR 4 = CH 2 (4-2)
^{_{H 2 N-R 3 -O-}} CO-CR 4 = CH 2 (4-3)
(In the above formula, R ³ and R ⁴ have the same meaning as in the general formula (4).)

On the other hand, the silane monomer represented by the general formula (5) includes a (meth) acryloyloxy compound containing an isocyanate group represented by the following general formula (5-1) and the following general formula (5-2). ) To (5-4) and a silane compound in the presence of a catalyst in the presence of a catalyst, as in the known method described in Embodiment 1, and then synthesized by a urethane reaction, a urea reaction, or a urea reaction. Can do.
^{_{CH 2 = CR 4 -CO-O}} -R 3 -N = C = O (5-1)
(In the above formula, R ³ and R ⁴ have the same meaning as in the general formula (5).)

(R ¹ O) ₃ Si—R ² —OH (5-2)
(R ¹ O) ₃ Si—R ² —SH (5-3)
(R ¹ O) ₃ Si—R ² —NH ₂ (5-4)
(In the above formula, R ¹ and R ² have the same meaning as in the general formula (5)).

Among these, the silane monomer represented by the general formula (4) is preferable.
The reason for this is that these functional groups in a (meth) acryloyloxy compound containing functional groups such as thiol groups, primary amino groups, and secondary amino groups that react with isocyanates are isocyanates of the silane compound having an isocyanate group. The urethane bond by reaction with the group is easily formed selectively, the reaction with the unsaturated group in the (meth) acryloyloxy group is unlikely to be synthesized, and this structure is effective for improving the adhesion. And so on. In addition, when these functional groups of a (meth) acryloyloxy compound having a functional group such as a thiol group, a primary amino group, and a secondary amino group that react with an isocyanate group are a thiol group or an amino group, a color filter is used. This is because it is considered that it is difficult to remain as a residue on the substrate at the time of alkali development during production, and that the urethane bond site in the general formula (4) is considered to work particularly effectively for improving the adhesion to the substrate.

  The silane monomer of the general formula (4) or (5) may be used alone or as a mixture of monomers obtained by mixing a plurality of types of monomers. Alternatively, these monomers may be hydrolyzed to obtain oligomers and used. These may be used by mixing with other alkoxysilane monomers or oligomers. Alternatively, the monomer of the general formula (4) or (5) and another alkoxysilane monomer may be hydrolyzed to obtain an oligomer, which may be used.

  The silane monomer represented by the general formula (4) or (5) may be used in the same form as in the second, third, and fourth embodiments.

<Board adhesion effect under high temperature and high humidity>
The structure of the general formula (1) brings about an effect of improving the adhesion between the substrate and the cured film, particularly under high temperature and high humidity. The action is considered as follows.

First, by having a silane site, the silanol group is adsorbed by the interaction of the polar group of the substrate with hydrogen bonds and the like, and the alkoxy group is also converted into a silanol group by hydrolysis due to the action of moisture under high humidity. Similarly, it is considered that the adhesion with the substrate is improved by the adsorption. In particular, when the substrate is a glass substrate, it is considered that hydrogen bonds with silanol groups on the surface of the glass substrate and that a strong chemical bond is formed by a dehydration reaction at a high temperature.
Such a strong bond can be obtained when the color filter is manufactured under conditions of high humidity and high temperature during the coating and drying process, during the alkaline developer processing, or during the high temperature heat treatment of 200 ° C. or higher. Later, it is also formed during overseas transportation and use under high humidity and high temperature.

Moreover, the urethane bond part in the said General formula (1-1) is a carboxyl group, ester group, an epoxy acrylate group, etc. which are contained in alkali-soluble resin in a photosensitive resin composition, a photopolymerizable monomer, a dispersing agent, etc. It is considered that the photosensitive resin composition and the substrate are more firmly adhered to each other through the organosilicon compound (f-1) by bonding with the polar group through hydrogen bonding or charge interaction.
This effect is synergistically improved especially when the photopolymerizable monomer has an ester bond or the dispersant has a urethane bond.

  Furthermore, the unsaturated group in the general formula (1-1) is cross-linked to the alkali-soluble resin in the photosensitive resin composition or the unsaturated group in the photopolymerizable monomer by ultraviolet irradiation or high heat treatment during the production of the color filter. I think that. In particular, when the photopolymerization initiator in the photosensitive resin composition contains a highly sensitive material such as an oxime ester, the effect is considered to be synergistically improved.

  Thus, due to the synergistic effect of the silane moiety in the general formula (1), the urethane bond site in the general formula (1-1), and the unsaturated group moiety, the substrate and the photosensitive resin composition It is considered that the adhesion is greatly improved.

<Board adhesion effect at room temperature>
The structure of the general formula (1) is effective in improving the adhesion between the substrate and the cured film even at room temperature, and the action is considered as follows.

  The adhesion effect with the substrate surface due to the presence of the silane moiety tends to be less than the effect under high temperature and high humidity, but it is treated with water contained in the photosensitive resin composition or an alkali developing aqueous solution. Moisture that is sometimes taken into the substrate surface or the photosensitive layer is then post-baked at a high temperature of 200 ° C. or more, thereby being hydrolyzed and improving the adhesion to the substrate. Further, due to the synergistic effect of the urethane bond site and the unsaturated group site, the adhesion between the substrate and the photosensitive composition is greatly improved by the organosilicon compound of the present application even at room temperature.

<Alkali-soluble resin (a)>
The photosensitive resin composition of this invention contains alkali-soluble resin (a). The alkali-soluble resin (a) is coated with a photopolymerizable monomer (b), a photopolymerization initiator (c), a colorant (d), and a photosensitive resin composition containing an organosilicon compound (f) and dried. Although it will not specifically limit if the solubility with respect to the alkali image development of an exposure part and a non-exposed part changes after exposing the cured film obtained by this, It is preferable that it is alkali-soluble resin which has a carboxyl group. Moreover, what has an ethylenically unsaturated group is preferable, and alkali-soluble resin which has an ethylenically unsaturated group and a carboxyl group is still more preferable. Specific examples include an epoxy (meth) acrylate resin and an acrylic copolymer resin having a carboxyl group, and more preferable examples are (A1-1), (A1-2), (A2- Examples include 1), (A2-2), (A2-3) and (A2-4), and these may be used alone or in combination of two or more. Among the above, epoxy (meth) acrylate resins (A1-1) and (A1-2) having a carboxyl group are particularly desirable.

  When creating a color filter, a polymer resin having an acidic functional group such as a hydroxyl group, a carboxyl group, a phosphoric acid group, or a sulfonic acid group is used as the polymer resin in order to dissolve the non-exposed portion in the alkaline developer. The Among these, from the viewpoint of solubility in an alkaline developer, a polymer resin having a carboxyl group is preferable. In addition, although phosphoric acid groups and sulfonic acid groups have higher acidity than carboxyl groups, they easily react with initiators, monomers, dispersants and other additives having basic groups in the photosensitive resin composition. , Storage stability may deteriorate.

  In addition, the organosilicon compound (f-1) having a urethane bond site represented by the general formula (1) is bonded to a polar group such as a carboxyl group in an alkali-soluble resin by a hydrogen bond or a charge interaction. The adhesion between the photosensitive resin composition and the substrate tends to be further improved.

  Furthermore, the organosilicon compound (f-1) having an unsaturated group represented by the general formula (1) includes an ethylenically unsaturated group in an alkali-soluble resin, ultraviolet irradiation during color filter production, and high heat treatment. Sometimes they tend to crosslink with each other and further improve adhesion to the substrate.

  In addition, when an epoxy acrylate resin is used as an alkali-soluble resin having a carboxyl group and an ethylenically unsaturated group, it becomes possible to add more unsaturated bonds and carboxyl groups in the resin, and the aromatic ring It is possible to include a large amount of structure or a three-dimensionally bulky alicyclic structure, and the interaction with the organosilicon compound (f-1) is further increased, and the adhesion to the substrate is further improved. There is a tendency to further improve.

Examples of the epoxy (meth) acrylate resin having a carboxyl group include the following epoxy (meth) acrylate resin (A1-1) and / or epoxy (meth) acrylate resin (A1-2).
<Epoxy (meth) acrylate resin (A1-1)>
It was obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Alkali-soluble resin.
<Epoxy (meth) acrylate resin (A1-2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this.

(Epoxy (meth) acrylate resin (A1-1) having carboxyl group and ethylenically unsaturated group bond)
As an epoxy resin used as a raw material, for example, bisphenol A type epoxy resin (for example, “Epicoat (registered trademark; the same applies hereinafter) 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004” manufactured by Mitsubishi Chemical Corporation, etc. ), Epoxy obtained by reaction of alcoholic hydroxyl group of bisphenol A type epoxy resin and epichlorohydrin (for example, “NER-1302” manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, softening point 76 ° C.)), bisphenol F type resin ( For example, “Epicoat 807”, “EP-4001”, “EP-4002”, “EP-4004 etc.” manufactured by Mitsubishi Chemical Corporation), an epoxy resin obtained by the reaction of an alcoholic hydroxyl group of bisphenol F type epoxy resin with epichlorohydrin (For example, “NER-7 manufactured by Nippon Kayaku Co., Ltd. 06 ”(epoxy equivalent 350, softening point 66 ° C.)), bisphenol S type epoxy resin, biphenyl glycidyl ether (eg“ YX-4000 ”manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (eg Nippon Kayaku Co., Ltd.) "EPPN-201" manufactured by Mitsubishi Chemical Corporation, "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Co., Ltd.), (o, m, p-) cresol novolac type epoxy resin (For example, “EOCN (registered trademark) manufactured by Nippon Kayaku Co., Ltd.”) “102S”, “EOCN-1020”, “EOCN-104S”), triglycidyl isocyanurate (for example, “TEPIC manufactured by Nissan Chemical Co., Ltd.) (Registered trademark) ”), trisphenolmethane type epoxy resin (for example,“ EPPN (registered trademark) manufactured by Nippon Kayaku Co., Ltd. ) -501 "," EPN-502 "," EPPN-503 "), cycloaliphatic epoxy resin (" Celoxide (registered trademark, the same applies hereinafter) 2021P "," Celoxide EHPE "manufactured by Daicel Chemical Industries, Ltd.) , An epoxy resin obtained by glycidylation of a phenol resin by reaction of dicyclopentadiene and phenol (for example, “EXA-7200” manufactured by Dainippon Ink and “NC-7300” manufactured by Nippon Kayaku Co., Ltd.), the following general formula (a1 The epoxy resins represented by (a4) to (a4) can be suitably used. Specifically, “XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (a1) and “XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (a2) As an epoxy resin represented by “NC-3000” and the following general formula (a4), “ESF-300” manufactured by Nippon Steel Chemical Co., Ltd. may be mentioned.

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

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

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

In the general formulas (a3-1) and (a3-2), R ^{31 to} R ³⁴ and R ^{35 to} R ³⁷ are each independently an adamantyl group, a hydrogen atom, or a substituent which may have a substituent. The alkyl group of C1-C12 which may have this, or the phenyl group which may have a substituent is shown. Moreover, * mark in a formula represents the binding site in (a3).

In the general formula (a4), p and q each independently represent an integer of 0 to 4, and R ⁴¹ and R ⁴² each independently represent an alkyl group or a halogen atom. R ⁴³ and R ⁴⁴ each independently represents an alkylene group. x and y each independently represents an integer of 0 or more.
Among these, it is preferable to use an epoxy resin represented by any one of the general formulas (a1) to (a4).

Examples of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, (meta ) Monocarboxylic acid such as α-position haloalkyl, alkoxyl, halogen, nitro, cyano substituent of acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( (Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- ( (Meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- (meth) a Acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) acryloyl Loxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid,
The (meth) acrylic acid ester is a single monomer having one hydroxyl group at the terminal by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone to (meth) acrylic acid. Body,
Alternatively, a monomer having one hydroxyl group at the end, such as hydroxyalkyl (meth) acrylate, or a compound having one hydroxyl group at the end, such as pentaerythritol tri (meth) acrylate, is added to (anhydrous) succinic acid, (Meth) acrylic acid ester having one or more ethylenically unsaturated groups and one carboxyl group at the end by adding an acid (anhydride) such as (anhydrous) phthalic acid or (anhydrous) maleic acid . Moreover, (meth) acrylic acid dimer etc. are also mentioned.

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

In addition, 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 alone or in combination of two types. You may use the above together.
The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of epoxy resin. More preferably, it is in the range of 0.7 to 1.1 equivalents.
If the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is small, the amount of unsaturated groups introduced is insufficient, and the subsequent polybasic acid and / or anhydride thereof The reaction with is also insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, when the amount used is large, α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.

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

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

  A known method can be used for addition reaction of polybasic acid and / or anhydride thereof, and α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid having carboxyl group to epoxy resin. The target product can be obtained by continuing the reaction under the same conditions as in the ester addition reaction. The addition amount of the polybasic acid and / or its anhydride component is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mg KOH / g, and further 20 It is preferable that it is a grade which becomes the range of -140 mgKOH / g. When the acid value of the carboxyl group-containing epoxy (meth) acrylate resin is less than the above range, the alkali developability tends to be poor, and when it exceeds the above range, the curing performance tends to be poor.

((A1-1) Synthesis of Resin and (A1-1) Synthesis of Resin with Addition of Polyhydric Alcohol to Resin and Introduced Branch Structure)
In the addition reaction synthesis of the polybasic acid and / or anhydride thereof of the (A1-1) resin, polyhydric alcohol such as trimethylolpropane, pentaerythritol, dipentaerythritol is added, and a multi-branched structure is introduced. Also good.
The carboxyl group-containing epoxy (meth) acrylate resin is usually a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group. Or after mixing the anhydride, or a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group with a polybasic acid and / or Or it is obtained by heating after mixing the anhydride and polyhydric alcohol. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyhydric alcohol is not particularly limited. Any hydroxyl group present in the mixture of the reaction product of the epoxy resin and the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group and the polyhydric alcohol by heating. To the polybasic acid and / or its anhydride.

The carboxyl group-containing epoxy (meth) acrylate resin may be used alone or as a mixture of two or more resins.
If the amount of polyhydric alcohol is too small, the effect is thin, and if it is too large, there is a possibility of thickening or gelation. Therefore, a carboxyl group is added to the epoxy resin component and the α, β-unsaturated monocarboxylic acid or ester moiety. It is about 0.01-0.5 mass times normally with respect to the reaction material with the (alpha), (beta)-unsaturated monocarboxylic acid ester component which has, Preferably it is about 0.02-0.2 mass times.

  The acid value of the epoxy (meth) acrylate resin (A1-1, A1-2) thus obtained is usually 10 mgKOH / g or more, preferably 50 mgKOH / g or more. If the acid value is less than 10 mgKOH / g, developability may be insufficient. If the acid value is excessively high, there is a problem with the alkali resistance of the photosensitive resin composition (that is, the alkaline developer may cause roughening of the pattern surface or film loss). Is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.

  The weight average molecular weight (Mw) in terms of polystyrene as measured by gel permeation chromatography (GPC) of the epoxy (meth) acrylate resin (A1-1, A1-2) is preferably 1,000 or more, and 1,500. More preferably. Further, it is preferably 10,000 or less, more preferably 8,000 or less, and still more preferably 6,000 or less. If the weight average molecular weight is too small, there may be a problem in sensitivity, coating strength, and alkali resistance, and if it is too large, a problem may occur in developability and re-solubility.

(Acrylic copolymer resin (A2-1) (A2-2) (A2-3) (A2-4)
Examples of the acrylic copolymer resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, and JP-A-2000-56118. Various polymer compounds described in JP-A-2003-233179, JP-A-2007-270147, and the like can be used. Preferably, the following (A2-1) to (A2-) 4) resin etc. are mentioned, Among these, (A2-1) resin is particularly preferable.

(A2-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. A resin obtained by addition or a resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction (hereinafter sometimes referred to as “(A2-1) resin”).
(A2-2): Linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter sometimes referred to as “(A2-2) resin”)
(A2-3): Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the (A2-2) resin (hereinafter may be referred to as “(A2-3) resin”).
(A2-4): (Meth) acrylic resin (hereinafter sometimes referred to as “(A2-4) resin”)
The resin (A2-1) is also included in the concept of epoxy (meth) acrylate resin.
Hereinafter, each of these resins will be described.

<(A2-1) With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Resin obtained by addition or resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction>
More specifically, the resin (A2-1) is based on a copolymer of “epoxy group-containing (meth) acrylate 5 to 90 mol% and other radical polymerizable monomer 10 to 95 mol%. , A resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol% of the epoxy group of the copolymer, or a polybasic acid anhydride to 10 to 100 mol% of a hydroxyl group generated by the addition reaction And a resin obtained by adding "."

  (A2-1) Examples of the “epoxy group-containing (meth) acrylate” constituting the resin include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl ( Examples include meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

  As another radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate, mono (meth) acrylate having a structure represented by the following general formula (11) is preferable.

In the general formula (11), R ^{81 to} R ⁸⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁸⁷ and R ⁸⁸ are connected to each other to form a ring. May be.
In the general formula (11), the ring formed by connecting R ⁸⁷ and R ⁸⁸ is preferably an aliphatic ring, which may be saturated or unsaturated, and has 5 to 6 carbon atoms. Is preferred.

  Especially, as a structure represented by the said General formula (11), the structure represented by following formula (11a), (11b), or (11c) is preferable.

By introducing these structures into the alkali-soluble resin, when the photosensitive resin composition of the present invention is used for a color filter or an image display device, its heat resistance and strength can be enhanced.
Various mono (meth) acrylates having the structure represented by the general formula (11) can be used as long as they have the structure, and those represented by the following general formula (12) are particularly preferable.

(In the general formula (12), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the general formula (11).)
In the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer, the repeating unit derived from the mono (meth) acrylate having the structure represented by the general formula (11) is: Among repeating units derived from “other radical polymerizable monomers”, those containing 5 to 90 mol% are preferable, and those containing 15 to 50 mol% are particularly preferable.

The “other radical polymerizable monomer” other than the mono (meth) acrylate having the structure represented by the general formula (11) is not particularly limited.
(A2-1) As a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer of the resin, 5 to 90 mol of repeating units derived from the epoxy group-containing (meth) acrylate % And repeating units derived from other radical polymerizable monomers are preferred, and those comprising 30 to 70 mol% of the former and 70 to 30 mol% of the latter are particularly preferred.

In the (A2-1) resin, an unsaturated monobasic acid (polymerizable component) is added to the epoxy group portion of the copolymer of the above-mentioned epoxy resin-containing (meth) acrylate and another radical polymerizable monomer, The polybasic acid anhydride is reacted.
Various “unsaturated monobasic acids” to be added to the epoxy group can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond. Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, or p-vinylbenzoic acid, the α-position is substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These may be used alone or in combination of two or more.

By adding such components, it is possible to impart polymerizability to the (A2-1) resin.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 50 to 100 mol%.
Furthermore, various things can be used as "polybasic acid anhydride" added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of the copolymer.

  For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and succinic anhydride are preferred. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

By adding such a component, alkali solubility can be imparted to the (A2-1) resin.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 30 to 80 mol. %.

<(A2-2) Linear alkali-soluble resin containing a carboxyl group in the main chain>
(A2-2) The resin is not particularly limited as long as it has a carboxyl group, and is usually obtained by polymerizing a polymerizable monomer containing a carboxyl group.
Examples of the carboxyl group-containing polymerizable monomer include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl adipic acid. 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2- ( (Meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxybutyl Succinic acid, 2- (me ) Vinyl monomers such as acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid; -Monomers obtained by adding lactones such as caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone; hydroxyalkyl (meth) acrylate to succinic acid, maleic acid, phthalic acid, or anhydrides thereof And monomers added with acids or anhydrides. These may be used alone or in combination of two or more.

Among these, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is more preferable.
Moreover, (A2-2) resin may be obtained by copolymerizing the above carboxyl group-containing polymerizable monomer with another polymerizable monomer having no carboxyl group.
In this case, the other polymerizable monomer is not particularly limited, and examples thereof include those described in JP-A-2009-52010. Of these polymerizable monomers, a copolymer resin containing benzyl (meth) acrylate is particularly preferred from the viewpoint of excellent pigment dispersibility.

<(A2-3) Resin in which epoxy group-containing unsaturated compound is added to carboxyl group of (2-2) resin>
In the (A2-3) resin, the epoxy group-containing unsaturated compound to be added to the carboxyl group portion of the (A2-2) resin is particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule. Is not to be done.

  Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl). -4-Glycidyl) benzylacrylamide, acyclic epoxy group-containing unsaturated compounds such as 4-hydroxybutyl (meth) acrylate glycidyl ether can be mentioned, from the viewpoint of heat resistance and pigment dispersibility, The alicyclic epoxy group-containing unsaturated compounds described are preferred.

  Here, as the alicyclic epoxy group of the alicyclic epoxy group-containing unsaturated compound, for example, 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 7,8-epoxy [tricyclo [5.2. 1.0] dec-2-yl] group and the like. Further, the ethylenically unsaturated group is preferably derived from a (meth) acryloyl group.

<(A2-4) (Meth) acrylic resin>
Examples of the (A2-4) resin include a (meth) acrylic resin obtained by polymerizing a monomer component essentially containing a compound represented by the following general formula (6).

In the general formula (6), R ⁷¹ and R ⁷² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
Hereinafter, the compound of General formula (6) is explained in full detail.
In the ether dimer represented by the general formula (6), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ⁷¹ and R ⁷² is not particularly limited. A linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; an aryl group such as phenyl; Cycloaliphatic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; alkoxy groups such as 1-methoxyethyl and 1-ethoxyethyl A substituted alkyl group; an alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like, and a substituent having a primary or secondary carbon atom that is difficult to be removed by heat are preferable from the viewpoint of heat resistance. R ⁷¹ and R ⁷² may be the same type of substituent or different substituents.

In particular, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2 '-[oxybis ( Methylene)] bis-2-propenoate, dibenzyl-2,2 '-[oxybis (methylene)] bis-2-propenoate are preferred.
These ether dimers may be used alone or in combination of two or more.

The ratio of the ether dimer in the monomer component when obtaining the (A2-4) resin is not particularly limited, but is usually 2 to 60% by mass, preferably 5 to 50% by mass in all monomer components.
(A2-4) The resin preferably has an acid group. By having an acid group, the photosensitive resin composition of the present invention obtained using the acid group has a cross-linking reaction (hereinafter referred to as “acid-epoxy curing”) in which an acid group and an epoxy group react to form an ester bond. The photosensitive resin composition can be cured, or the photosensitive resin composition can be visualized with an alkaline developer in the uncured portion. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups contained in one molecule of resin may be only one kind or two or more kinds.

  (A2-4) In order to introduce an acid group into the resin, for example, a monomer having an acid group and / or a “monomer capable of imparting an acid group after polymerization” (hereinafter referred to as “monomer for introducing an acid group”) May be used as the monomer component. In addition, when using "monomer which can provide an acid group after superposition | polymerization" as a monomer component, the process for providing an acid group as mentioned later is required after superposition | polymerization.

Examples of the monomer having an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; maleic anhydride and itaconic anhydride. Although the monomer etc. which have a carboxylic anhydride group are mentioned, Especially, (meth) acrylic acid is preferable among these.
Examples of the monomer capable of adding an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; monomers having an epoxy group such as glycidyl (meth) acrylate; 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate.

These monomers for introducing an acid group may be used alone or in combination of two or more. (A2-4) When the monomer component for obtaining the resin also includes a monomer for introducing the acid group, the content is usually 5 to 70% by mass, preferably 10 to 60%, based on the total monomer components. % By mass.
(A2-4) The monomer component for obtaining the resin may contain other copolymerizable monomers as required in addition to the essential monomer component.

As above-mentioned, the photosensitive resin composition of this invention is (A1-1), (A1-2), (A2-1), (A2-2), (A2-3), (A2) as alkali-soluble resin. -4) is preferably included.
The photosensitive resin composition of the present invention contains at least one of (A1-1), (A1-2), (A2-1), and (A2-3) as an alkali-soluble resin containing an ethylenically unsaturated group. It is more preferable to include. The photosensitive resin composition of the present invention particularly preferably contains at least one of (A1-1) and (A1-2) which are epoxy acrylate resins as an alkali-soluble resin containing an ethylenically unsaturated group.

The photosensitive resin composition of the present invention may be used in combination with other alkali-soluble resins.
There is no restriction | limiting in other alkali-soluble resin, What is necessary is just to select from resin normally used for the photosensitive resin composition for color filters. Examples thereof include alkali-soluble resins described in JP2007-271727A, JP2007-316620A, JP2007-334290A, and the like.

Content of alkali-soluble resin (a) is 5 mass% or more normally with respect to the total solid of the photosensitive resin composition of this invention, Preferably it is 10 mass% or more, Usually 85 mass% or less, Preferably 80% by mass or less. When the content of the alkali-soluble resin (a) is remarkably small, the solubility of the unexposed portion in the developer tends to be lowered, and development failure tends to be induced. On the other hand, if the content of the alkali-soluble resin (a) is too large, the permeability of the developer into the exposed area tends to be high, and the sharpness and adhesion of the pixel may be lowered.
In addition, as above-mentioned, the photosensitive resin composition of this invention is the above-mentioned (A1-1), (A1-2), (A2-1), (A2-2) as alkali-soluble resin (a). , (A2-3) and (A2-4) are preferably included, and when other alkali-soluble resin is included, the content ratio is 20 mass with respect to the total of the alkali-soluble resin (a). % Or less, preferably 10% by mass or less.
As the alkali-soluble resin (a), (A1-1), (A1-2), (A2-1) and (A2-3) having an ethylenically unsaturated group are more preferable. As the alkali-soluble resin (a), (A1-1) and (A1-2) which are epoxy acrylate resins having an ethylenically unsaturated group are particularly preferable. These resins may be used alone or in combination of two or more.

<Photopolymerizable monomer (b)>
The photosensitive resin composition of this invention contains a photopolymerizable monomer (b) from points, such as a sensitivity.
Examples of the photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter sometimes referred to as “ethylenic monomer”). Specifically, for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, a monoester of polyhydric or monohydric alcohol, etc. Can be mentioned.

In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule.
Examples of such polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatics Examples thereof include esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a polyhydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.

  Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. In the same way, itaconic acid ester instead of itaconate, Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to and the like.

Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. Etc.
The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include acrylic acid, phthalic acid, and Examples include condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

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

  In particular, from the viewpoint of adhesion to the substrate, the photopolymerizable monomer (b) used in the present invention preferably contains a compound represented by any one of the following general formulas (b1) to (b4).

In the above formula, R ^b is a group represented by the following formula (b5), and R ⁹ is an alkylene group having 1 to 10 carbon atoms, an arylene alkylene group having 7 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms. is there.

In the above formula, R ⁶ represents an alkylene group which may have a branch having 2 to 6 carbon atoms in the main chain, and R ⁷ represents a hydrogen atom or a methyl group. m represents an integer of 0 to 3. When m is 2 or 3, the plurality of R ⁶ may be the same or different.

R ⁸ in the general formula (b3) is an alkyl group having 1 to 6 carbon atoms, and from the viewpoint of adhesion to the substrate, the carbon number is usually 1 or more, preferably 2 or more, and preferably 5 Below, more preferably 4 or less. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 1-pentyl, 1-hexyl, and cyclohexyl. Among these, from the viewpoint of adhesion to the substrate, a methyl group or an ethyl group is preferable, and an ethyl group is more preferable.

In the general formula (b4), the carbon number of the alkylene group represented by R ⁹ is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 3 or less, from the viewpoint of adhesion to the substrate. . Examples of the alkyl group having 1 to 10 carbon atoms include:
Methylene group, ethylene group, 1,3-propylene group, 1,2-propylene group, 1,4-butylene group, 1,2-butylene group, 1,5-pentylene group, 1,6-hexylene group, cyclohexylene Group, methylenecyclohexylene group, and the like, among these, from the viewpoint of adhesion to the substrate, a methylene group, an ethylene group, or a 1,3-propylene group is preferable, and an ethylene group is more preferable.
In the general formula (b4), the number of carbon atoms of the arylene alkylene group of R ⁹ is preferably 7 or more and preferably 9 or less from the viewpoint of adhesion to the substrate. Examples of the arylene alkylene group having 7 to 10 carbon atoms include a phenylenemethylene group, a phenyleneethylene group, and a phenylenepropylene group. Among these, from the viewpoint of adhesion to the substrate, a phenylenemethylene group or A phenyleneethylene group, more preferably a phenylenemethylene group.
In the general formula (b4), the number of carbon atoms of the arylene group of R ⁹ is preferably 6 or more and preferably 10 or less from the viewpoint of adhesion to the substrate. Examples of the arylene group having 6 to 10 carbon atoms include a phenylene group and a naphthylene group. Among these, a phenylene group is preferable from the viewpoint of adhesion to a substrate.
Among these, from the viewpoint of adhesion to the substrate, R ⁹ is preferably a methylene group, an ethylene group, or a propylene group, and more preferably an ethylene group.

In the general formula (b5), R ⁶ represents an alkylene group which may have a branch having 2 to 6 carbon atoms in the main chain. From the viewpoint of adhesion to the substrate, the number of carbon atoms is preferably 3 or more. 4 or more is more preferable, 6 or less is preferable, and 5 or less is more preferable. The alkylene group may or may not have a branch, but it is preferably not branched from the viewpoint of adhesion to the substrate. Examples of the alkylene group that may have 2 to 6 carbon atoms in the main chain include a methylene group, an ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 1,4-butylene group, Examples include 1,2-butylene group, 1,3-butylene group, 1,5-pentylene group, 1,2-pentylene group, 1,3-pentylene group, 1,6-hexylene group, cyclohexylene group and the like. Among these, from the viewpoint of adhesion to the substrate, 1,4-butylene group or 1,5-pentylene group is preferable, and 1,5-pentylene group is more preferable.

m represents an integer of 0 to 3. The general formulas (b1) to (b4) include a plurality of R ^b groups, and the R ^b groups may be the same or different. From the viewpoint of adhesion to the substrate, R ^b are preferably different from each other, more preferably m have R ^b groups. Specifically, an R ^b group in which m is 0 (hereinafter abbreviated as R ^b1 group) and an integer R ^b group in which m is 1 to 3 (hereinafter abbreviated as R ^b2 group). It is preferable to have. Note that m in the R ^b2 group is preferably 1 or 2 and more preferably 1 from the viewpoint of adhesion to the substrate.

Of R ^b group contained more in the general formula (b1), it is preferable that at least one is R ^b2 group, and more preferably at least two are R ^b2 group.
Of R ^b group contained more in the general formula (b2), it is preferable that at least one is R ^b2 group, and more preferably at least two are R ^b2 group.
Of R ^b group contained more in the general formula (b3), it is preferable that at least one is R ^b2 group, and more preferably at least two are R ^b2 group.
Of R ^b group contained more in the general formula (b4), it is preferable that at least one is R ^b2 group, and more preferably at least two are R ^b2 group.

In the photosensitive resin composition of the present invention, the reason why the photopolymerizable monomer (b) preferably contains such a specific compound is as follows.
Such a specific compound is considered to interact with a polar group such as a silanol group of the glass substrate by the polar component of the polyester structure to improve the adhesion to the substrate. Furthermore, this specific compound is crosslinked with an organosilicon compound (f-1) having an unsaturated group of (meth) acryloyloxy group during ultraviolet irradiation or high heat treatment at the time of producing a color filter, and further increases the adhesion to the substrate. It is thought that it can be improved.
In addition, the urethane bonding site in the organosilicon compound (f-1) can also be bonded to the polar component of the polyester structure in the specific compound by hydrogen bonding or charge interaction, thereby further improving the adhesion. It is considered possible.

  In the compounds represented by the general formulas (b1) to (b4), a lactone is added to a part or all of the hydroxyl groups of the polyhydric alcohols represented by the following general formulas (b1 ′) to (b4 ′), It can then be obtained by (meth) acrylation.

In said formula, R < ⁸ > and R < ⁹ > is synonymous with the said general formula (a3) and (a4).

  Examples of lactones to be added to polyhydric alcohol include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, δ-valerolactone, α, α-dimethyl- Examples include γ-butyrolactone, ε-caprolactone, δ-hexanolactone, γ-hexanolactone, and γ-heptanolactone. Among these, γ-butyrolactone, δ-valerolactone, and ε-caprolactone are preferable, and ε-caprolactone is particularly preferable.

  The photopolymerizable monomer (b) of the compound represented by any one of these general formulas (b1) to (b4) may be used alone or in combination with a plurality of compounds. Moreover, it can also be used in combination with a photopolymerizable monomer other than the compound having a structure represented by any one of the general formulas (b1) to (b4) such as pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate. However, when using together photopolymerizable monomers other than the compound of the structure represented by either of general formula (b1)-(b4), general formula (b1)-(in photopolymerizable monomer (b) ( The proportion of the photopolymerizable monomer other than the compound having the structure represented by any of b4) is preferably 50% by mass or less, particularly preferably 0 to 25% by mass.

  The ratio of the photopolymerizable monomer (b) is usually 90% by mass or less, preferably 80% by mass or less, based on the total solid content of the photosensitive resin composition. When the content of the photopolymerizable monomer is not more than the above upper limit, the permeability of the developer into the exposed area becomes appropriate, and a good image tends to be obtained. The lower limit of the content of the photopolymerizable monomer (b) is usually 1% by mass or more, preferably 5% by mass or more. By being more than the said minimum, it exists in the tendency for the photocuring by ultraviolet irradiation to improve, and for alkali developability to also become favorable.

<Photopolymerization initiator (c)>
The photopolymerization initiator is a component having a function of directly absorbing light and causing a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical. If necessary, an additive such as a sensitizing dye may be added and used.

  Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197, and hexaarylbi compounds described in JP-A-2000-56118. Imidazole derivatives; N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in JP-A-10-39503, N-aryl-α-amino acid salts, Radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester derivatives described in JP 2000-80068 A, JP 2006-36750 A, and the like. .

  Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny 1-yl), dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclone) Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-difluoro-3- (pyro-1-yl) -phen-1-yl] and the like. Can be mentioned.

  Biimidazole 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′-methoxy) Phenyl) -4,5-diphenylimidazole dimer and the like.

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

  Examples of 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.

  Examples of α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoe -To, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like It is.

As photopolymerization initiators, oxime derivatives (oxime-based and ketoxime-based compounds) are particularly effective in terms of sensitivity, and are disadvantageous in terms of sensitivity when using an alkali-soluble resin containing a phenolic hydroxyl group. In some cases, oxime derivatives (oxime-based and ketoxime-based compounds) excellent in such sensitivity are particularly useful. Among oxime derivatives, oxime esters are preferable from the viewpoint of adhesion to a substrate.
The photopolymerization initiator of oxime ester has both a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals. Therefore, it is possible to design a photosensitive resin composition that is stable and sensitive in a small amount. In particular, in the case of an oxime ester containing a carbazole group, this structural property is well expressed and more preferable. Currently, the market demands a high degree of shading, a thin BM (black matrix), and the pigment concentration is also increasing. In such a situation, it is particularly effective.

  As described above, the organosilicon compound (f-1) has an unsaturated group of (meth) acryloyloxy group, which is unsaturated in an alkali-soluble resin or photopolymerizable monomer contained in the photosensitive resin composition. It is considered that the adhesiveness with the substrate can be greatly improved by crosslinking with the group at the time of ultraviolet irradiation at the time of manufacturing the color filter or at the time of high heat treatment. In particular, when the initiator in the photosensitive resin composition contains an oxime ester having the above characteristics, the effect is considered to be synergistically improved.

  Examples of the oxime compound include a compound including a structural moiety represented by the following general formula (22), and preferably include an oxime ester compound represented by the following general formula (23).

In the above formula (22), R ²² is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and a carbon number. 3 to 8 cycloalkanoyl group, 3 to 20 alkoxycarbonylalkanoyl group, 8 to 20 phenoxycarbonylalkanoyl group, 3 to 20 heteroaryloxycarbonylalkanoyl group, 2 to 10 carbon atoms An aminoalkylcarbonyl group, an aryloyl group having 7 to 20 carbon atoms, a heteroarylloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms;

(In formula (23), R ^21a is hydrogen or an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a heteroarylalkyl group having 1 to 20 carbon atoms. , C3-C20 alkoxycarbonylalkyl group, C8-C20 phenoxycarbonylalkyl group, C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, C1-C20 aminoalkyl Group, alkanoyl group having 2 to 12 carbon atoms, alkenoyl group having 3 to 25 carbon atoms, cycloalkanoyl group having 3 to 8 carbon atoms, aryloyl group having 7 to 20 carbon atoms, heteroarylloyl group having 1 to 20 carbon atoms, C2-C10 alkoxycarbonyl group, C7-C20 aryloxycarbonyl group, or C1-C10 A chloroalkylalkyl group is shown.
R ^21b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.

R ^21a may form a ring together with R ^21b , and each of the linking groups thereof may have a substituent, an alkylene group having 1 to 10 carbon atoms, a polyethylene group (— (CH═CH) _r. -), A polyethynylene group (-(C≡C) _r- ) or a group formed by a combination thereof (where r is an integer of 0 to 3).
R ^22a represents the same group as R ²² in the above formula (22).
R ²² in the general formula (22) and R ^22a in the general formula (23) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and 3 to 8 carbon atoms. Of the cycloalkanoyl group.

R ^21a in the general formula (23) is preferably substituted with a linear alkyl group such as an unsubstituted methyl group, ethyl group or propyl group or a cycloalkylalkyl group, or an N-acetyl-N-acetoxyamino group. And propyl group.
In addition, R ^21b in the general formula (23) is preferably an optionally substituted carbazole group, an optionally substituted thioxanthonyl group, or an optionally substituted phenyl sulfide group.

As the oxime ester photopolymerization initiator (c), those containing a carbazole group which may be substituted as R ^21b are more preferable for the reasons described above. Furthermore, an aryl group having 6 to 25 carbon atoms which may be substituted, an arylcarbonyl group having 7 to 25 carbon atoms which may be substituted, a heteroaryl group having 5 to 25 carbon atoms which may be substituted, and substitution A carbazole group having at least one group selected from the group consisting of a heteroarylcarbonyl group having 6 to 25 carbon atoms and a nitro group which may be used is preferable. In particular, a carbazole group having at least one group selected from the group consisting of a benzoyl group, a toluoyl group, a naphthoyl group, a thienylcarbonyl group, and a nitro group is preferable. These groups are preferably bonded to the 3-position of the carbazole group.

  Commercially available products of such oxime ester photopolymerization initiator (c) include OXE-02 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Power Electronics.

  Specific examples of the oxime ester photopolymerization initiator (c) include compounds exemplified below as oxime ester compounds suitable for the present invention, but the oxime ester photopolymerization initiator (c) is not limited to these compounds. .

  Examples of the ketoxime compound include a compound containing a structural moiety represented by the following general formula (24), and preferably an oxime ester compound represented by the following general formula (25).

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

(In the above general formula (25), each R ^23a may be a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a heteroaryl having 1 to 20 carbon atoms. An alkyl group, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms, or heteroary Ruthioalkyl group, C1-C20 aminoalkyl group, C2-C12 alkanoyl group, C3-C25 alkenoyl group, C3-C8 cycloalkanoyl group, C7-C20 aryloyl group , A C1-C20 heteroaryloyl group, a C2-C10 alkoxycarbonyl group, a C7-C2 0 aryloxycarbonyl group or a C1-C10 cycloalkylalkyl group is shown.

R ^23b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
R ^23a may form a ring together with R ^23b , and the linking group thereof may have an optionally substituted alkylene group having 1 to 10 carbon atoms or a polyethylene group (— (CH═CH) _r. -), A polyethynylene group (-(C≡C) _r- ) or a group formed by a combination thereof (where r is an integer of 0 to 3).

R ^24a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, carbon Heteroaryloyl group having 3 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, heteroaryl group having 2 to 20 carbon atoms, or alkylamino having 2 to 20 carbon atoms Represents a carbonyl group. )
R ²⁴ in the general formula (24) and R ^24a in the general formula (25) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and 3 to 8 carbon atoms. And a cycloalkanoyl group and an aryloyl group having 7 to 20 carbon atoms.

R ^23a in the general formula (25) is preferably an unsubstituted ethyl group, propyl group, butyl group, or an ethyl group or propyl group substituted with a methoxycarbonyl group.
In addition, R ^23b in the general formula (25) is preferably an optionally substituted carbazoyl group or an optionally substituted phenyl sulfide group.
Specific examples of the ketoxime ester-based compound suitable for the present invention include compounds exemplified below, but the ketoxime ester-based compound is not limited to these compounds.

  Commercially available products of such oxime ester photopolymerization initiator (c) include OXE-01 manufactured by BASF, TR-PBG-305 manufactured by Changzhou Strong Electronic Co., Ltd.

These oxime and ketoxime ester compounds are known compounds per se, and are, for example, one of a series of compounds described in JP-A No. 2000-80068 and JP-A No. 2006-36750.
The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.

Other benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone Benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, benzophenone derivatives such as 2-carboxybenzophenone; 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenol Nylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) -2-morpholino-1 Acetophenone derivatives such as propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (p- Methoxyph Yl) acridine derivatives acridine like; 9,10-dimethyl-benz phenazine phenazine derivatives such as; anthrone derivatives such as benzanthrone etc. may be mentioned.
Among these photopolymerization initiators, oxime ester derivatives are particularly preferable for the reasons described above.

<Sensitizing dye>
If necessary, the photopolymerization initiator can be used in combination with a sensitizing dye according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. These sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and 3-ketocoumarin compounds described in Kaihei 3-239703 and 5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A 47-2528, 54-155292, JP 45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-6988, JP-A-57-168088. No. 5, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818. Mention may be made of a dye or the like having a skeleton.

Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-diethyl Aminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, (p -Dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. and p-dialkylaminophenyl group-containing compounds.
Of these, 4,4′-dialkylaminobenzophenone is most preferred.
A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.

Content of a photoinitiator (c) is 0.1 mass% or more normally with respect to the total solid of the photosensitive resin composition of this invention, Preferably it is 0.5 mass% or more, More preferably, it is 0.00. It is 7 mass% or more, and is 30 mass% or less normally, Preferably it is 20 mass% or less. When the content of the photopolymerization initiator (c) is too small, the sensitivity may be lowered. On the other hand, when the content is too large, the solubility of the unexposed portion in the developer is lowered, and development failure is likely to be induced.
In particular, the proportion of the oxime ester in the photopolymerization initiator (c) is usually 10% by mass or more, preferably 50% by mass or more, more preferably 90% by mass or more. By setting it to the above lower limit or more, when combined with the organosilicon compound (f-1) of the present invention and an alkali-soluble resin as the photosensitive resin composition of the present application, the adhesion to the substrate is further improved after ultraviolet irradiation. There is a tendency to be able to.

  When using an accelerator with a photoinitiator (c), content of an accelerator is 0 mass% or more normally with respect to the total solid of the photosensitive resin composition of this invention, Preferably it is 0.02 mass%. In the above, it is usually 10% by mass or less, preferably 5% by mass or less. It is preferable to use in. When the blending ratio of the photopolymerization initiator component composed of the photopolymerization initiator (c) and the accelerator is extremely low, the sensitivity to the exposure light may be lowered. The solubility in the liquid may be reduced, leading to poor development.

  Moreover, when using a sensitizing dye, the compounding ratio of the sensitizing dye in the photosensitive resin composition of this invention is 0-20 mass% normally in the total solid in the photosensitive resin composition, Preferably it is 0-0. It is 15 mass%, More preferably, it is 0-10 mass%.

<Coloring material (d)>
The photosensitive resin composition of the present invention contains a coloring material when used for forming a pixel of a color filter, a black matrix, or the like. A coloring material means what colors the photosensitive resin composition of this invention. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like.

  As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is.

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

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

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

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

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

Moreover, when the photosensitive resin composition of this invention is the photosensitive resin composition for resin black matrices of a color filter, a black coloring material can be used as a coloring 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 can be appropriately selected from inorganic or organic pigments and dyes.
Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean the color index (CI)).

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

Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black.
Among these color materials (d), when a black color material is used as the photosensitive resin composition, carbon black is preferable from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black.

  Mitsubishi Chemical Corporation: MA7, MA77, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350 # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B Made by Degussa: Printex (registered trademark; The same.) 3, Printex3OP, Printex30, Printex30OP, Print x40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color black FW200, Color Black S160, Color Black S170 Cabot: Monarch (registered trademark; the same applies hereinafter) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1100, Monarch 1100, Monarch 1100, Monarch1100, Monarch1100, Monarch1100, Monarch1100, Monarch1100 The same shall apply hereinafter.) 99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark) -8

Made by Colombian Carbon: Raven11, Raven14, Raven15, Raven16, Raven22, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven890, Raven1000, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10 RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
As examples of other black pigments, titanium black, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments.

Carbon black coated with a resin may be used. Use of carbon black coated with a resin has the effect of improving adhesion to a glass substrate and volume resistance. As carbon black coated with resin, for example, carbon black described in JP-A No. 09-71733 can be suitably used.
As carbon black to be coated, the total content of Na and Ca is preferably 100 ppm or less. Carbon black is usually raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulated water, Na mixed from furnace materials of the reactor, Ca, K, Mg, Al, Fe, etc. Is contained in the order of percent. Of these, Na and Ca are generally contained in a few hundred ppm or more, but if many of these are present, they penetrate into the transparent electrode (ITO) and other electrodes, causing electrical shorts. This is because there is a case.

  As a method for reducing the content of ash containing these Na and Ca, carefully select those with as little content as possible as raw oil, fuel oil (or gas) and reaction stop water when producing carbon black. This is possible by reducing the addition amount of the alkaline substance for adjusting the structure as much as possible. As another method, carbon black produced from the furnace is washed with water, hydrochloric acid or the like, and Na or Ca is dissolved and removed.

  In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, or the like can also be used as the pigment. These various pigments can be used in combination. For example, in order to adjust chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

<Particle particle size>
The average particle diameter of the pigment used in the present invention is not particularly limited as long as it can produce a desired color when it is used as a colored layer of a color filter, and varies depending on the type of pigment used. It is preferably in the range of ˜100 nm, more preferably in the range of 10 to 70 nm. When the average particle diameter of the pigment is within the above range, the color characteristics of the liquid crystal display device produced using the photosensitive resin composition of the present invention can be made high quality.
In addition, when the pigment is carbon black, the average particle diameter of the pigment is preferably 60 nm or less, and more preferably 50 nm or less. Further, when the pigment is carbon black, the average particle diameter of the pigment is preferably 20 nm or more. If the pigment becomes too large, scattering increases and color characteristics such as light shielding properties and contrast tend to deteriorate. On the other hand, if the pigment particle size is too small, a large amount of dispersant is required, and the dispersibility tends to decrease.
In addition, the average particle diameter of the pigment can be obtained by a method of directly measuring the size of primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle are measured, and the average is taken as the particle diameter of the particle. Next, for 100 or more particles, the volume (mass) of each particle is obtained by approximating a cuboid with the obtained particle size, and the volume average particle size is obtained and used as the average particle size. The same result can be obtained regardless of whether the electron microscope is a transmission type (TEM) or a scanning type (SEM).

  Moreover, although it is preferable that the photosensitive resin composition of this application contains a pigment at least, you may use a dye together in the range which does not affect the effect of this application. Examples of dyes that can be used in combination include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

  Content of a coloring material (d) can be normally selected in 1-70 mass% with respect to the total solid content in the photosensitive resin composition. In this range, 20 mass% or more is more preferable, 40 mass% or more is more preferable, and 70 mass% or less is more preferable.

  The photosensitive resin composition of the present invention can be used for various applications as described above, but excellent image forming properties are particularly effective when used for forming a black matrix for a color filter. . When using it for forming a black matrix, use a black color material such as carbon black or titanium black described above as the color material (d), or mix several types of color materials other than black and adjust to black. It ’s fine. Among these, it is particularly preferable to use carbon black.

  The present invention is particularly effective in the region where the pigment concentration of the black pigment increases. Particularly in recent years, it is necessary to increase the black pigment concentration in order to increase the degree of light shielding. The content of the black pigment in the region where the effect is large is a region of 40% by mass or more with respect to the solid content of the colored photosensitive resin composition. The effect is greater when it is 45% by mass or more, and the effect can be further enhanced when it is 50% by mass or more.

  In the photosensitive resin composition, a colored photosensitive resin composition having a high light-shielding property (optical density, OD value) can be obtained by containing the black pigment within the above-described content range. Specifically, by setting the black pigment content to 45% by mass or more, the optical density when the black matrix having a thickness of 1 μm is formed using the photosensitive resin composition of the present invention is 4.0 or more. Can be a value. The optical density is more preferably 4.2 or more. In regions with high light shielding properties, ultraviolet rays are difficult to penetrate deeper, and crosslinking due to photopolymerization is weak particularly in the area where the substrate and fine wires are in close contact, but the pigment concentration is particularly high when the photosensitive resin composition of the present application is used. When it is large, the effect of the present application can be confirmed well. A pigment concentration of 40 to 65% by mass is particularly effective. If the content of the color material is too small, the film thickness with respect to the color density becomes too large, which may adversely affect the gap control during liquid crystal cell formation. On the other hand, if the content of the color material is too large, sufficient image formability may not be obtained.

  In the photosensitive resin composition, the amount relative to the colorant (d) is usually 20 to 500 parts by weight, preferably 30 to 300 parts by weight, more preferably 40 to 200 parts by weight per 100 parts by weight of the alkali-soluble resin (a). Part range. If the content of the alkali-soluble resin (a) with respect to the color material (d) is too low, the solubility of the unexposed portion in the developing solution is lowered and development failure is likely to be induced. It tends to be difficult to obtain.

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

  Examples of polymer dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ethers. Examples thereof include a dispersant, a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

Specific examples of such a dispersant are trade names of EFKA (registered trademark, manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (registered trademark, manufactured by BYK Chemie), and Disparon (registered trademark, Enomoto Kasei). , SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow or Florene (registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Fine Techno Co., Ltd. Etc.).
These polymer dispersants may be used alone or in combination of two or more.

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

  As described above, the organosilicon compound (f-1) of the present invention has a synergistic action of its organosilane site, urethane bond site, and ethylenically unsaturated group site, so that it can be used at high temperature and high humidity or at room temperature. Improves adhesion between the cured product and the substrate. It is considered that the urethane bond site of the organosilicon compound (f-1) can form a bond with the urethane bond site of the urethane-based polymer dispersant with an affinity such as hydrogen bond, and can further improve the adhesion to the substrate. It is done. Therefore, urethane polymer dispersants are particularly preferred in the present invention.

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less, and particularly preferably 30,000 or less. When the weight average molecular weight is 30,000 or less, the alkali developability tends to be good even when the pigment concentration is high.
Examples of urethane-based and acrylic polymer dispersants include Disperbyk 160 to 167, 182 series (both are urethane-based), Disperbyk 2000, 2001, etc. (both are acrylic-based) (all manufactured by Big Chemie). Disperbyk 167, 182 and the like are preferable as a urethane polymer dispersant having a basic functional group and having a polyester and / or polyether bond and having a weight average molecular weight of 30,000 or less.

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

  Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω Alicyclic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as luxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate , Triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, and trimers thereof, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

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

  Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. A mixture of two or more of the above.

  Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, , 6-hexanediol, 2-methyl-2,4- Nanthanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N -N-alkyl dialkanolamines such as methyldiethanolamine) obtained by polycondensation, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diol or carbon number 1 to 25 monovalent Polylactone diol or polylactone monool obtained by using an alcohol as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone initiated with an alcohol having 1 to 25 carbon atoms.

Examples of polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Is mentioned.
These may be used alone or in combination of two or more.

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

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, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.
Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  In addition, when the tertiary amino group is a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocyclic ring include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo N-containing hetero 5-membered ring such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, etc., nitrogen-containing hetero 6-membered ring such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring A ring is mentioned. Among these nitrogen-containing heterocycles, preferred are an imidazole ring or a triazole ring.

  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. Further, specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole preferable.

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

  Manufacture of a urethane type polymer dispersing agent is performed in accordance with the well-known method of polyurethane resin manufacture. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used. These may be used alone or in combination of two or more.

  In the above production, a urethanization reaction catalyst is usually used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. 1 type, or 2 or more types, such as a secondary amine type | system | group, are mentioned.

<Method of measuring amine value>
The tertiary amine value of the dispersant is represented by the mass of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and can be measured by the following method.
Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO ₄ (perchloric acid) acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S)
[However, W: Weighing amount of dispersant sample [g], V: Titration amount at the end of titration [mL], S: Solid content concentration [mass%] of the dispersant sample. ]
The amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mgKOH / g. The amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amine value is lower than the above range, the dispersing ability tends to be lowered, and when it exceeds the above range, the developability tends to be lowered.

In addition, when an isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time is increased.
The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. In particular, 30,000 or less is preferable. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility tends to be low and the dispersibility is poor, and at the same time, the reaction tends to be difficult to control. When the molecular weight is 30,000 or less, alkali developability tends to be good even when the pigment concentration is particularly high. Examples of such a particularly preferred commercially available urethane dispersant include Disperbyk 167 and 182 (Bic Chemie).

(Acrylic polymer dispersant)
As the acrylic polymer dispersant, an unsaturated group-containing monomer having a functional group (the functional group here is the functional group described above as the functional group contained in the polymer dispersant); It is preferable to use a random polymer, a graft copolymer, or a block copolymer with an unsaturated group-containing monomer having no functional group. These copolymers can be produced by a known method.

  Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acrylic acid. Tertiary amino groups such as unsaturated monomers having a carboxyl group such as leuoxyethyl hexahydrophthalic acid and acrylic acid dimer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof; Specific examples include unsaturated monomers having a quaternary ammonium base. These may be used alone or in combination of two or more.

  Examples of the unsaturated group-containing monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohe N-substituted maleimides such as silmaleimide, N-phenylmaleimide, N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly-2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol Examples thereof include macromonomers, polypropylene glycol macromonomers, and macromonomers such as polycaprolactone macromonomers. These may be used alone or in combination of two or more.

(Acrylic block copolymer)
In the photosensitive resin composition of the present invention, an acrylic block copolymer containing a nitrogen atom may be used as a dispersant in order to improve the dispersibility of the colorant and the dispersion stability. Such an acrylic block copolymer containing nitrogen atoms has a nitrogen atom contained therein having an affinity for the colorant surface, and a portion other than the nitrogen atom increases the affinity for the medium as a whole. It is estimated that it contributes to the improvement of dispersion stability.
The performance of a dispersant is its adsorption behavior on the solid surface. The reason why the block copolymer is excellent in adsorption behavior is not clear in detail, but the following is presumed.

  That is, in the case of a normal random copolymer, it is highly likely that the monomer constituting the copolymer is stably arranged in the copolymer sterically and / or electrically during the copolymerization. . Since the portion (molecule) in which the monomer is stably arranged is sterically and / or electrically stable, it may be an obstacle when adsorbing to the colorant. On the other hand, in a resin whose molecular arrangement is controlled, such as a block copolymer, a portion that prevents adsorption of the dispersant can be disposed at a position away from the adsorption portion of the pigment and the dispersant. That is, an optimum portion for adsorption can be arranged in the adsorbing portion between the colorant and the dispersing agent, and a portion suitable for it can be arranged in a portion requiring solvent affinity. In particular, the dispersion of a coloring material containing a colorant having a small crystallite size is presumed that this molecular arrangement affects the good dispersibility.

  An acrylic block copolymer containing a nitrogen atom is preferable in that the colorant used in the present invention can be dispersed very efficiently. The reason is not clear, but it is presumed that because the molecular arrangement is controlled, there are few structures that obstruct the dispersing agent when adsorbed to the colorant. As an acrylic block copolymer, an AB block copolymer comprising an A block having a quaternary ammonium base and / or amino group in a side chain and a B block having no quaternary ammonium base and amino group. And / or B-A-B block copolymers are preferred.

When the A block has a quaternary ammonium base, the quaternary ammonium base is preferably —N ⁺ R ⁵¹ R ⁵² R ⁵³ · M ⁻ (where R ⁵¹ , R ⁵² and R ⁵³ are each independently hydrogen Represents an atom or a cyclic or chain hydrocarbon group which may be substituted, or two or more of R ⁵¹ , R ⁵² and R ⁵³ may be bonded to each other to form a cyclic structure; M ⁻ represents a counter anion. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

In -N ⁺ R ⁵¹ R ⁵² R ⁵³ , as the cyclic structure formed by combining two or more of R ⁵¹ , R ⁵² and R ⁵³ with each other, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or A condensed ring formed by condensing two of these may be mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following. These cyclic structures may further have a substituent.

In the above formula, R represents any group of R ^{51 to} R ⁵³ .
As R ⁵¹ to R ⁵³ in ^{-N + R 51 R 52 R 53} , more preferably it may have an alkyl group, or a substituent having carbon atoms of 1 to 3 may have a substituent It is a phenyl group or a benzyl group which may have a substituent.
As the A block having a quaternary ammonium base, those containing a partial structure represented by the following general formula (VI) are particularly preferable.

In the above formula (VI), R ⁵¹ , R ⁵² , and R ⁵³ each independently represent a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, two or more of R ⁵¹ , R ⁵² and R ⁵³ may be bonded to each other to form a cyclic structure. R ⁵⁴ represents a hydrogen atom or a methyl group. X represents a divalent linking group, and M ⁻ represents a counter anion.
In the general formula (VI), the hydrocarbon groups of R ⁵¹ , R ⁵² , and R ⁵³ are each independently a substituent having an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 20 carbon atoms. preferable. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, and a phenyl group. Of these, a methyl group, an ethyl group, a propyl group, and a benzyl group are preferable.

In the general formula (VI), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R ⁵⁵ —, —COO—R ⁵⁶ — (provided that R ⁵⁵ and R ⁵⁶ represents a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R ⁵⁷ —O—R ⁵⁸ —: R ⁵⁷ and R ⁵⁸ are each independently an alkylene group). Represents.)
Etc., and preferably —COO—R ⁵⁶ —.

Examples of the counter anion M ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .
Two or more kinds of partial structures containing the specific quaternary ammonium base as described above may be contained in one A block. In that case, two or more quaternary ammonium base-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base may be contained in the A block, and examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later. It is done.

The content of the partial structure containing no quaternary ammonium base in the A block is preferably 0 to 50% by mass, more preferably 0 to 20% by mass. Most preferably, it is not included in the A block.
In addition, the A block of the acrylic block copolymer described above may have an unreacted tertiary amino group that is not quaternized.

When the A block has an amino group, the amino group may be any of primary to tertiary. The content ratio of the monomer having the primary to tertiary amino group is preferably 20 mol% or more, more preferably 50 mol in the monomer composition constituting the acrylic block copolymer. % Or more.
This amino group may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

The primary to tertiary amino group is preferably —NR ⁶¹ R ⁶² (wherein R ⁶¹ and R ⁶² are each independently a cyclic or chain alkyl group which may have a substituent, An aryl group which may have a substituent or an aralkyl group which may have a substituent is preferable. As a partial structure including this (repeating unit), preferred examples include the following: A structure represented by the general formula can be given.

However, R ⁶¹ and R ⁶² have the same meanings as R ⁶¹ and R ⁶² described above, R ⁶³ represents an alkylene group having 1 or more carbon atoms, and R ⁶⁴ represents a hydrogen atom or a methyl group.
Among them, R ⁶¹ and R ⁶² are preferably a methyl group, R ⁶³ is preferably a methylene group or an ethylene group, and R ⁶⁴ is preferably a hydrogen atom or a methyl group. As such a partial structure, a structure derived from dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate represented by the following general formula is particularly preferably used.

In the above general formula, R ⁶⁴ has the same meaning as described above.
Furthermore, the partial structure containing the said amino group may be contained 2 or more types in one A block. In that case, two or more types of amino group-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. A partial structure not containing an amino group may be partially contained in the A block, and examples of such a partial structure include a partial structure derived from a (meth) acrylic acid ester monomer. . The content in the A block of the partial structure not containing such an amino group is preferably 0 to 50% by mass, more preferably 0 to 20% by mass, but such an amino group-free partial structure is present in the A block. Most preferably it is not included.

The A block may have either one of a quaternary ammonium base or an amino group, or may have both.
On the other hand, the B block constituting the acrylic block copolymer has no quaternary ammonium base and amino group as described above, and is composed of a monomer that can be copolymerized with the monomer constituting the A block as described above. There is no particular limitation. The B block is a solvophilic site that does not have a nitrogen atom-containing functional group serving as a pigment adsorbing group, and has an affinity for the solvent, and thus has a function of stabilizing the pigment adsorbed on the dispersant in the solvent. .

  Examples of the B block include styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic. Acid butyl, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, N, N-dimethylaminoethyl (Meth) acrylate monomers such as (meth) acrylate; (meth) acrylate monomers such as (meth) acrylic chloride; (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N , N-di Vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether, (meth) acrylamide monomers such as chill aminoethyl acrylamide N- methacryloyl morpholine, polymer structure obtained by copolymerizing comonomers such.

  As the B block, one containing a partial structure derived from a (meth) acrylic acid ester monomer represented by the following formula (VIII) is particularly preferable.

In the above formula (VIII), R ⁶¹ represents a hydrogen atom or a methyl group. R ⁶² represents a cyclic or chain alkyl group which may have a substituent, an allyl group which may have a substituent, or an aralkyl group which may have a substituent.
Two or more kinds of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block. Of course, the B block may further contain a partial structure other than these. When a partial structure derived from two or more monomers is present in a B block that does not contain a quaternary ammonium base, each partial structure is contained in the B block in any form of random copolymerization or block copolymerization. May be.

When the B block contains a partial structure other than the partial structure derived from the (meth) acrylate monomer, the content in the B block of the partial structure other than the (meth) acrylate monomer is preferably Is 0 to 99 mass%, more preferably 0 to 85 mass%.
The acrylic dispersant used in the present invention is an AB block or a B-A-B block copolymer type polymer compound composed of such an A block and a B block, and such a block copolymer. Is prepared, for example, by a living polymerization method.

The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. For example, the method described in JP2007-270147A can be mentioned.
The amine value of the acrylic block copolymer is usually about 1 to 300 mgKOH / g in terms of effective solid content, but the preferred range is when the A block has a quaternary ammonium base and when it does not. It is different. The amine value is a value expressed in mg of KOH corresponding to the molar equivalent of acid necessary for neutralizing the amino group in 1 g of the copolymer.

That is, in the AB block copolymer and the B-A-B block copolymer according to the present invention, when the A block has a quaternary ammonium base, the amount of the quaternary ammonium base in 1 g of the copolymer is Usually, it is preferably 0.1 to 10 mmol, and outside this range, it may not be possible to combine good heat resistance and dispersibility.
Such a block copolymer usually contains an amino group produced in the production process, but its amine value is usually about 1 to 100 mgKOH / g, preferably 1 to 80 mgKOH / g. . More preferably, it is 1-50 mgKOH / g.

When the quaternary ammonium base is not included in the A block, the amine value of the copolymer is usually about 50 to 300 mgKOH / g, preferably 50 to 200 mgKOH / g, more preferably 80 mgKOH / g or more and 150 mgKOH / g. Hereinafter, it is more preferably 90 to 150 mgKOH / g.
The acid value of such an acrylic block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but generally it is preferably lower, usually 100 mgKOH / g or less, preferably 50 mgKOH / g. g or less, more preferably 40 mgKOH / g or less.

The molecular weight of the acrylic block copolymer is usually in the range of 1000 or more and 100,000 or less in terms of polystyrene-reduced weight average molecular weight (Mw) measured by GPC. When the molecular weight of the acrylic block copolymer is too small, the dispersion stability decreases, and when it is too large, the developability and resolution tend to decrease.
In the present invention, a commercially available acrylic block copolymer having the same structure as described above can also be applied.

(Graft copolymer containing nitrogen atoms)
As the graft copolymer containing a nitrogen atom, those having a repeating unit containing a nitrogen atom in the main chain are preferred. Especially, it is preferable to have a repeating unit represented by the following general formula (i) or / and a repeating unit represented by the following general formula (ii).

(In the general formulas (i) and (ii), R ⁹¹ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably an alkylene having 2 to 3 carbon atoms. A group, more preferably an ethylene group, A represents a hydrogen atom or any one of the following general formulas (iii) to (v), preferably the following general formula (iii).

（一般式（ｉｉｉ）中、Ｗ¹は炭素数２〜１０の直鎖状又は分岐状のアルキレン基を表し、中でもブチレン、ペンチレン、ヘキシレン等の炭素数４〜７のアルキレン基が好ましい。ｐは１〜２０の整数を表し、好ましくは５〜１０の整数である。）

(In General Formula (iii), W ¹ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and among them, an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene, and hexylene is preferable. Represents an integer of 1 to 20, preferably an integer of 5 to 10.)

（一般式（ｉｖ）中、Ｇ¹は２価の連結基を表し、中でもエチレン、プロピレン等の炭素数１〜４のアルキレン基とエチレンオキシ、プロピレンオキシ等の炭素数１〜４のアルキレンオキシ基が好ましい。Ｗ²はエチレン、プロピレン、ブチレン等の直鎖状又は分岐状の炭素数２〜１０のアルキレン基を表し、中でもエチレン、プロピレン等の炭素数２〜３のアルキレン基が好ましい。Ｇ²は水素原子又は−ＣＯ−Ｒ⁹²（Ｒ⁹²はエチル、プロピル、ブチル、ペンチル、ヘキシル等の炭素数１〜１０のアルキル基を表し、中でもエチル、プロピル、ブチル、ペンチル等の炭素数２〜５のアルキル基が好ましい）を表す。ｑは、１〜２０の整数を表し、好ましくは５〜１０の整数である。）

(In General Formula (iv), G ¹ represents a divalent linking group, and in particular, an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene and an alkyleneoxy group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy. preferably .W ² represents ethylene, propylene, a linear or branched alkylene group having 2 to 10 carbon atoms butylene, among which ethylene, an alkylene group having 2 to 3 carbon atoms such as propylene preferred .G ² Represents a hydrogen atom or —CO—R ⁹² (R ⁹² represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, etc., among them, C 2-5 such as ethyl, propyl, butyl, pentyl, etc. Q represents an integer of 1 to 20, preferably an integer of 5 to 10.)

（一般式（ｖ）中、Ｗ³は炭素数１〜５０のアルキル基又は水酸基を１〜５有する炭素数１〜５０のヒドロキシアルキル基を表し、中でもステアリル等の炭素数１０〜２０のアルキル基、モノヒドロキシステアリル等の水酸基を１〜２個有する炭素数１０〜２０のヒドロキシアルキル基が好ましい。）

(In general formula (v), W ³ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms having 1 to 5 hydroxyl groups, and in particular, an alkyl group having 10 to 20 carbon atoms such as stearyl. C1-C20 hydroxyalkyl groups having 1-2 hydroxyl groups such as monohydroxystearyl are preferred.)

The content of the repeating unit represented by the general formula (i) or (ii) in the graft copolymer containing a nitrogen atom is preferably higher, and is usually 50 mol% or more in total, preferably 70 mol%. That's it. The repeating unit represented by the general formula (i) and the repeating unit represented by the general formula (ii) may both be present, and the content ratio is not particularly limited, but is preferably the general formula ( It is preferable that the repeating unit i) is contained in a larger amount. The total number of repeating units represented by general formula (i) or general formula (ii) in the graft copolymer is 1 or more, preferably 10 or more, more preferably 20 or more, and usually 100 or less, preferably 70. Hereinafter, it is more preferably 50 or less. Further, the graft copolymer may contain a repeating unit other than the general formula (i) and the general formula (ii), and examples of the other repeating unit include an alkylene group and an alkyleneoxy group. The graft copolymer in the present invention preferably has —NH ₂ and —R ⁹¹ —NH ₂ (R ⁹¹ is as defined in formulas (i) and (ii)) at the ends.

  In the case of the graft copolymer as described above, the main chain may be linear or branched.

  The weight average molecular weight of the graft copolymer measured by GPC is preferably 3,000 or more, particularly 5,000 or more, and preferably 100,000 or less, particularly 50,000 or less. If the mass average molecular weight is less than 3,000, the color material cannot be aggregated, and may increase in viscosity or gel. If it exceeds 100,000, the viscosity itself increases. This is not preferable because the solubility in an organic solvent is insufficient.

  As a method for synthesizing the dispersing agent, a known method can be employed. For example, a method described in JP-B-63-30057 can be used.

  Content of a dispersing agent is 50 mass% or less normally in the solid content of the photosensitive resin composition, Preferably it is 30 mass% or less, Usually 1 mass% or more, Preferably it is 3 mass% or more. Further, the content of the dispersant is usually 5% by mass or more, particularly 10% by mass or more, and usually 200% by mass or less, and particularly preferably 80% by mass or less, with respect to the coloring material (d). If the content of the dispersant is too low, sufficient dispersibility may not be obtained. If the content is too high, the proportion of other components is relatively reduced, and the color density, sensitivity, film formability, etc. tend to decrease. is there.

In particular, it is preferable to use a polymer dispersant and a pigment derivative in combination as the dispersant. In this case, the blending ratio of the pigment derivative is usually 0 with respect to the total solid content of the photosensitive resin composition of the present invention. .1% by mass or more, usually 10% by mass or less, preferably 5% by mass or less.
When using surfactant, the content is 0.001-10 mass% normally with respect to the total solid in the photosensitive resin composition, Preferably it is 0.005-1 mass%, More preferably, it is 0.01. It is -0.5 mass%, Most preferably, it is 0.03-0.3 mass%. If the surfactant content is less than the above range, the smoothness and uniformity of the coating film may not be expressed. If the content is too high, the smoothness and uniformity of the coating film may not be expressed, and other characteristics deteriorate. There is a case. In addition, the photosensitive resin composition of this invention is prepared using the above-mentioned organic solvent so that the solid content concentration may become 5-50 mass% normally, Preferably it is 10-30 mass%.

<Thiols>
It is preferable to add thiols to the photosensitive resin composition of the present invention in order to increase sensitivity and improve adhesion to the substrate. Types of thiols include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate , Butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, Ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate); (PGMB for short), Diol (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane; (trade name; Karenz MT BD1, manufactured by Showa Denko KK), butanediol trimethylolpropane tris (3-mercapto) Butyrate), pentaerythritol tetrakis (3-mercaptobutyrate); (trade name; Karenz MT PE1, Showa Denko KK), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoiso) (Butyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptobutyrate); (TPMB for short) trimethylolpropane tris (2 Mercaptoisobutyrate); (TPMIB for short), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (Trade name; Karenz MT NR1, manufactured by Showa Denko Co., Ltd.) and the like, and various of these may be used alone or in combination of two or more. Preferred are polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, Karenz MT NR1, among which Karenz MT BD1, Karenz MT PE1 and Karenz MT NR1 are more preferable, and Karenz MT PE1 is Particularly preferred.

  When a thiol compound is used, the content of the thiol compound is usually 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0%, based on the total solid content of the photosensitive resin composition of the present invention. 0.5 mass or more, usually 10 mass% or less, preferably 5 mass% or less. When the content of the thiol compound is too small, the sensitivity may be lowered. On the other hand, when the content is too large, the storage stability may be deteriorated.

<Solvent>
The photosensitive resin composition of the present invention usually contains an alkali-soluble resin (a) containing an ethylenically unsaturated group, a photopolymerizable monomer (b), a photopolymerization initiator (c), a color material (d), a dispersion. The agent (e) and various materials used as necessary are used in a state dissolved or dispersed in an organic solvent.
As an organic solvent, it is preferable to select an organic solvent having a boiling point (under a pressure of 101.25 [hPa], hereinafter the same for boiling points) in the range of 100 to 300 ° C. More preferably, it is a solvent having a boiling point of 120 to 280 ° C.
Examples of such organic solvents include the following.

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

  Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxy Tyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol mono Glycol alkyl ether acetates such as ethyl ether acetate, 3-methyl-3-methoxybutyl acetate;

  Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, Ethers such as dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone , Methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Mono ketones such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol Aliphatic alcohols such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene and dodecane; alicyclic rings such as cyclohexane, methylcyclohexane, methylcyclohexene and bicyclohexyl Formula hydrocarbons;

  Aromatic hydrocarbons such as benzene, toluene, xylene, cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, Propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 3-methoxy Linear or cyclic esters such as ethyl propionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and gamma-butyrolactone; alkoxy groups such as 3-methoxypropionic acid and 3-ethoxypropionic acid Bonn acids;

  Halogenated hydrocarbons such as butyl chloride and amyl chloride; Ether ketones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrile, etc .: Examples of commercially available solvents corresponding to the above include mineral spirits and valsols # 2, Apco # 18 Solvent, Apco Thinner, Soak Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("Cerosolve" is a registered trademark, the same shall apply hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (any Product name).

These organic solvents may be used alone or in combination of two or more.
When a color filter pixel or black matrix is formed by photolithography, it is preferable to select an organic solvent having a boiling point in the range of 100 to 200 ° C. More preferably, it has a boiling point of 120 to 170 ° C.
Of the above organic solvents, glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension and the like, and relatively high solubility of the constituent components in the composition.

  In addition, glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability tends to decrease such as the viscosity of the photosensitive resin composition obtained later increases. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

  It is also preferable to use an organic solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as “high boiling point solvent”). By using such a high boiling point solvent together, the photosensitive resin composition becomes difficult to dry, but there is an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation or solidification of a color material or the like at the tip of the slit nozzle. Among these various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable because of such high effects.

  The content of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. If the amount of the high boiling point solvent is too small, for example, a coloring material may precipitate and solidify at the tip of the slit nozzle to cause a foreign matter defect, and if it is too much, the drying temperature of the composition will be slowed down. There is a concern that problems such as tact defects in the vacuum drying process and prebaked pin marks may be caused in the filter manufacturing process.

  The high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150 ° C. or higher is not separately contained. It doesn't matter. Preferred examples of the high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.

  In the photosensitive resin composition of the present invention, the content of the organic solvent is not particularly limited, but is preferably 5% by mass or more, more preferably 8% by mass or more, and still more preferably from the viewpoint of ease of application and viscosity stability. It is 10 mass% or more, Preferably it is 40 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 25 mass% or less.

<Other ingredients of the photosensitive resin composition>
In addition to the above-described components, the photosensitive resin composition of the present invention is appropriately mixed with an adhesion improver, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, a surfactant, a pigment derivative, and the like. Can do.

(Adhesion improver)
In order to improve the adhesion to the substrate, an adhesion improver other than the organosilicon compound (f) may be included in the photosensitive resin composition of the present invention. For example, a phosphate adhesion improver, other adhesion enhancement Agents and the like.

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

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

(Surfactant)
The photosensitive coloring composition of the present invention may contain a surfactant in order to improve coatability. As the surfactant, for example, various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among these, nonionic surfactants are preferably used because they are less likely to adversely affect various properties, and among them, fluorine-based and silicon-based surfactants are effective in terms of coatability.

Examples of such surfactants include TSF4460 (manufactured by GE Toshiba Silicone), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), and KP340 (Shin-Etsu Silicone). F-470, F-475, F-478, F-559 (Dainippon Ink & Chemicals), SH7PA (Toray Silicone), DS-401 (Daikin), L-77 Nippon Unicar Co., Ltd.), FC4430 (Sumitomo 3M Co., Ltd.) and the like.
In addition, 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.

[Other ingredients]
In addition to the above-mentioned components, the light-shielding photosensitive resin composition of the present invention further includes a polymerization accelerator, a photoacid generator, a crosslinking agent, a plasticizer, a storage stabilizer, a surface protective agent, an organic carboxylic acid, an organic carboxylic acid. An acid anhydride, a development improver, a thermal polymerization inhibitor and the like may be contained.
(Pigment derivative)
The photosensitive coloring composition of the present invention may contain a pigment derivative for improving dispersibility and storage stability. As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Among them, derivatives such as phthalocyanines and quinophthalones are preferable.

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

<Method for producing photosensitive resin composition>
The photosensitive resin composition of the present invention (hereinafter sometimes referred to as “resist”) is produced according to a conventional method.
Usually, it is preferable to disperse the color material (d) in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since the color material (d) is finely divided by the dispersion treatment, the resist coating characteristics are improved. Further, when a black color material is used as the color material (d), it contributes to an improvement in light shielding ability.

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

  When the color material (d) is dispersed with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. In the dispersion treatment conditions, the temperature is usually from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus. The standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the resist is in the range of 100 to 200. When the glossiness of the resist is low, the dispersion treatment is not sufficient, and rough pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, and the like. . Further, when the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.

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

[Cured product]
A cured product can be obtained by curing the photosensitive resin composition of the present invention. A cured product obtained by curing the photosensitive resin composition can be suitably used as a black matrix or a colored spacer.

[Black Matrix]
Next, the black matrix using the photosensitive resin composition of the present invention will be described in accordance with its production method.

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

The support may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc., if necessary, in order to improve surface properties such as adhesion. .
The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

(2) Black matrix In order to form the black matrix of the present invention by the above-described photosensitive resin composition of the present invention, the photosensitive resin composition of the present invention is applied on a transparent substrate and dried, and then the sample is coated. A black mask is formed by placing a photomask on the substrate and exposing the image through the photomask, developing, and thermosetting or photocuring as necessary.

(3) Formation of black matrix (3-1) Application of photosensitive resin composition Application of a photosensitive resin composition for a black matrix onto a transparent substrate is performed by a spinner method, a wire bar method, a flow coating method, or a die coating method. , Roll coating method or spray coating method. In particular, the die coating method significantly reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. To preferred.

  If the thickness of the coating film is too thick, pattern development becomes difficult, and it may be difficult to adjust the gap in the liquid crystal cell forming process. May become impossible. The thickness of the coating is usually preferably in the range of 0.2 to 10 μm as the film thickness after drying, more preferably in the range of 0.5 to 6 μm, and still more preferably in the range of 1 to 4 μm. is there.

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

The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, when the drying temperature is too high, the alkali-soluble resin is decomposed, and thermal polymerization may be induced to cause development failure. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.
(3-3) Exposure Image exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive resin composition and irradiating an ultraviolet light source or a visible light source through the mask pattern. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

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

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

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, 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.
There are no particular limitations on the conditions for the development treatment, and usually the development temperature is in the range of 10 to 50 ° C., especially 15 to 45 ° C., particularly preferably 20 to 40 ° C. The development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.

(3-5) Thermosetting treatment The substrate after development is subjected to thermosetting treatment or photocuring treatment, preferably thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes.
The black matrix formed as described above has a bottom width of usually 3 to 50 μm, preferably 4 to 30 μm, particularly 4 to 8 μm in the case of a high fine wire, and a height of usually 0.5 to 5 μm, preferably Is 1 to 4 μm. Further, the low volume efficiency is 1 × 10 ¹³ Ω · cm or more, preferably 1 × 10 ¹⁴ Ω · cm or more, and the relative dielectric constant is 6 or less, preferably 5 or less. Furthermore, the optical density (OD) per 1 μm thickness is 3.0 or more, preferably 3.5 or more, more preferably 4.0 or more, and particularly preferably 4.2 or more.

[Formation of other color filter images]
On a transparent substrate provided with a black matrix, a photosensitive colored resin composition containing a color material of one color of red, green, and blue is applied in the same process as the above (3-1) to (3-5), After drying, a photomask is overlaid on the coating film, and a pixel image is formed through image exposure, development, and heat curing or photocuring as necessary through this photomask to form a colored layer. A color filter image can be formed by performing this operation for each of the three colored photosensitive colored resin compositions of red, green, and blue. The order of these is not limited to the above.

[Coloring spacer]
The colored photosensitive composition of the present embodiment can be used as a resist for a colored spacer other than the black matrix. When a spacer is used for a TFT type LCD, the TFT may malfunction as a switching element due to light incident on the TFT, and a colored spacer is used to prevent this, for example, Japanese Patent Laid-Open No. 8-234212. Describes that the spacer is light-shielding. The colored spacer can be formed in the same manner as the black matrix described above except that a mask for the colored spacer is used.

(3-6) Formation of transparent electrode In this state, the color filter forms a transparent electrode such as ITO on the image and is used as a part of parts such as a color display and a liquid crystal display device. In order to enhance the property and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

[Image display device]
The image display device of the present invention is not particularly limited as long as it is a device that displays an image or video, and examples thereof include a liquid crystal display device and an organic EL display described later.
[Liquid Crystal Display]
The liquid crystal display device of the present invention is manufactured using the above-described black matrix of the present invention, and is not particularly limited in terms of formation order and formation position of color pixels and black matrix.

  A liquid crystal display device usually forms an alignment film on a color filter, spreads spacers on the alignment film, and then bonds to the counter substrate to form a liquid crystal cell, injects liquid crystal into the formed liquid crystal cell, Complete by connecting to the counter electrode. As the alignment film, a resin film such as polyimide is suitable. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.

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

The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of reduced pressure in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The warming hold during decompression is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.

The type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.
[Organic EL display]
The organic EL display of the present invention is produced using the color filter of the present invention.

  When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. A color filter in which a resin black matrix (not shown) provided between the pixels 20 is formed is manufactured, and the organic light-emitting body 500 is formed on the color filter via the organic protective layer 30 and the inorganic oxide film 40. By laminating, the organic EL element 100 can be manufactured. In addition, at least one of the pixel 20 and the resin black matrix is produced using the photosensitive colored resin composition of the present invention. As a method for laminating the organic light-emitting body 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. A method described in, for example, “Organic EL display” (Ohm, Inc., August 20, 2004, light emission, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) using the organic EL element 100 manufactured in this manner, etc. Thus, an organic EL display can be produced.

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

  Next, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.

<Adjustment of carbon black ink>
A pigment, a dispersant, a dispersion aid, and a solvent were prepared with the following composition, and a carbon black ink was prepared by the following method.
First, the solid content of the pigment, the dispersant, and the dispersion aid and the solvent were prepared so as to have the following quantitative ratio.
Pigment: R1060 (carbon black manufactured by Columbia); 100 parts by mass Dispersant: BYK167 (basic urethane dispersant manufactured by Big Chemie); 20 parts by mass (in terms of solid content)
Dispersing aid (pigment derivative): S12000 (manufactured by Lubrizol, phthalocyanine pigment derivative having an acidic group); 2.0 parts by mass; solvent; propylene glycol methyl ether acetate: 226.6 parts by mass

First, they were sufficiently stirred and mixed to obtain a dispersion.
Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As beads, zirconia beads having a diameter of 0.5 mm were used and added at a ratio of 180 parts by mass of beads to 60 parts by mass of the dispersion. After completion of the dispersion, the beads and the dispersion were separated by a filter to prepare a dispersion ink having a solid content of 35% by mass.

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

50 g of epoxy compound having the above structure (epoxy equivalent 264), 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of paramethoxyphenol were attached to a thermometer, a stirrer and a cooling pipe. The reaction was continued at 90 ° C. with stirring until the acid value was 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
25 parts by mass of the above epoxy acrylate solution, 0.76 parts by mass of trimethylolpropane (TMP), 3.3 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), 3.5 parts by mass of tetrahydrophthalic anhydride (THPA) Was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.
When the resin solution became transparent, it was diluted with methoxybutyl acetate and prepared to have a solid content of 50% by mass. Resin (1) was obtained.
<Synthesis Example 2: Synthesis of Photopolymerization Initiator (1)>

(Diketone body)
Ethylcarbazole (5 g, 25.61 mmol) and o-naphthoyl chloride (5.13 g, 26.89 mmol) are dissolved in 30 ml of dichloromethane, cooled to 2 ° C. with an ice-water bath and stirred, and then AlCl ₃ (3. 41 g, 25.61 mmol) was added. Further, after stirring at room temperature for 3 hours, a 15 ml dichloromethane solution of crotonoyl chloride (2.81 g, 26.89 mmol) was added to the reaction solution, then AlCl ₃ (4.1 g, 30.73 mmol) was added, and another 1 hour 30 hours. Stir for minutes. The reaction solution was poured into 200 ml of ice water, 200 ml of dichloromethane was added, and the organic layer was separated. The collected organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a diketone body as a white solid (10 g).

(Oxime body)
Diketone (3.00 g, 7.19 mmol), NH ₂ OH · HCl (1.09 g, 15.81 mmol), and sodium acetate (1.23 g, 15.08 mmol) were mixed with 30 ml of isopropanol and refluxed for 3 hours. .
After completion of the reaction, the reaction mixture was concentrated, 30 ml of ethyl acetate was added to the resulting residue, washed with 30 ml of saturated aqueous sodium hydrogen carbonate solution and 30 ml of saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the organic layer was concentrated under reduced pressure to obtain 1.82 g of a solid. This was purified by column chromatography to obtain 2.22 g of an oxime compound as a pale yellow solid.

(Oxime ester)
The oxime (2.22 g, 4.77 mmol) and acetyl chloride (1.34 g, 17.0 mmol) were added to 20 ml of dichloromethane, and the mixture was ice-cooled. Triethylamine (1.77 g, 17.5 mmol) was added dropwise, and 1 Reacted for hours. After confirming disappearance of the raw material by thin layer chromatography, water was added to stop the reaction. The reaction solution was washed twice with 5 ml of saturated aqueous sodium hydrogen carbonate solution and twice with 5 ml of saturated brine, and dried over anhydrous sodium sulfate. After filtration, the organic layer was concentrated under reduced pressure, and the resulting residue was purified by column chromatography (ethyl acetate / hexane = 2/1) to obtain 0.79 g of a light yellow solid photopolymerization initiator (1). Obtained. The chemical shift of ¹ H-NMR of the photopolymerization initiator (1) is shown below.

¹ H-NMR (CDCl ₃ ): σ 1.17 (d, 3H), 1.48 (t, 3H), 1.53 (s, 3H), 1.81 (s, 3H), 2.16 (s 3H), 2.30 (s, 3H), 3.17-3.32 (m, 2H), 4.42 (q, 2H), 4.78-4.94 (br, 1H), 7. 45-7.59 (m, 5H), 7.65 (dd, 1H), 7.95 (m, 2H), 8.04 (m, 2H), 8.14 (dd, 1H), 8.42 (D, 1H), 8.64 (d, 1H)

  The structure of the photopolymerization initiator (1) is as follows.

<Organic silicon compound>
The following organosilicon compounds 1 to 3 were prepared.
(Organic silicon compound 1)
The alkoxysilane monomer represented by the following formula (A), the dimer represented by the following formula (B), the trimer represented by the following formula (C), and the following formula (D) A mixture in which the weight ratio of the tetramer is 1: 14: 4: 1.

(Organic silicon compound 2)
The alkoxysilane monomer represented by the formula (A), the dimer represented by the formula (B), the trimer represented by the formula (C), and the formula (D). A mixture in which the weight ratio of the tetramer is 17: 1: 1: 1.

(Organic silicon compound 3)
The alkoxysilane monomer represented by the formula (A), the dimer represented by the formula (B), the trimer represented by the formula (C), and the formula (D). A mixture in which the weight ratio of the tetramer is 1: 8: 8: 3.

These organosilicon compounds are obtained by the method described in <Specific organosilicon compound (f)>.
These structures are identified by silica concentration using ¹ H-NMR, ¹³ C-NMR, IR and IPC light-emitting devices, elemental analysis of SEM-EDX, and the ratio of monomer, 2, 3, and tetramer. Was identified from the peak area separated by the liquid chromatogram and the parent ion peak of the mass spectrum of each peak.

⁽¹ H-NMR)
δ (ppm)
0.55 ppm (t, Si—CH ₂ , 2H)
1.55 ppm (m, —C—CH ₂ —C, 2H)
3.10 ppm (q, CH ₂ —N, 2H)
3.50 ppm (s, Si—OCH ₃ , about 9H)
4.25 ppm (s, O—CH ₂ —CH ₂ —O, about 4H)
5.10 ppm (s, N—H, 1H)
5.7-6.5 ppm (m, C (═O) CH═CH ₂ , 3H)

(IR spectrum)
Characteristic absorption (cm ^-1 )
3350 (N—H): 1726 (C═O): 1636, 1620 (C═C)

(Silica concentration by IPC light emitting device)
The sample was wet-ashed and alkali-melted, and then recovered and fixed with water. This aqueous solution was measured with an IPC light emitting device.
The Si concentration in the sample was 7.4% by mass.

  The presence of nitrogen element was confirmed by SEM-EDX analysis, and the molar ratio of nitrogen atom to Si atom was about 1: 1 by simple elemental analysis.

<Photopolymerizable monomer>
The following photopolymerizable monomers (b-I) to (b-V) were prepared.
bI: Acrylic ester compound 1 of dipentaerythritol caprolactone represented by the following structure (b11) (DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.))
b-II: Acrylic ester compound 2 of dipentaerythritol caprolactone represented by the following structure (b12) (DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.))
b-III: Acrylic ester compound 3 of dipentaerythritol caprolactone represented by the following structure (b13) (DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.))
b-IV Acrylic ester compound 4 of dipentaerythritol caprolactone represented by the following structure (b14) (DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.))
bV Acrylic ester compound 5 of pentaerythritol caprolactone represented by the following structure (b15) (manufactured by Shin-Nakamura Chemical Co., Ltd.)
b-VI Acrylic ester compound 6 of tris- (2-caprolactone ethyl) isocyanurate represented by the following structure (b16) (A-9300-1CL (manufactured by Shin-Nakamura Chemical Co., Ltd.))
b-VII Acrylic ester compound 7 of tris- (2-caprolactone ethyl) isocyanurate represented by the following structure (b17) (manufactured by Shin-Nakamura Chemical Co., Ltd.)

<Example 1>
(Preparation of black resist 1)
Using the carbon black ink prepared in <Adjustment of carbon black ink>, each component shown in Table 1 was added in the proportions shown in Table 1, and the mixture was stirred and dissolved with a stirrer to prepare black resist 1.

The details of the alkali-soluble resin (2) and dipentaerythritol hexaacrylate in the table are as follows.
Alkali-soluble resin (2): ZCR1642H. Epoxy acrylate resin (B1-1 resin) manufactured by Nippon Kayaku Co., Ltd. Synthesized by adding acrylic acid to biphenyl epoxy resin (Nippon Kayaku Co., Ltd., NC3000H) and reacting with tetrahydrophthalic anhydride. It has an ethylenically unsaturated group and a carboxylic acid group. Acid value 99 mgKOH / g, weight average molecular weight (Mw) 6400 in terms of polystyrene measured by GPC. Dipentaerythritol hexaacrylate: KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.

<Examples 2-3>
(Preparation of black resist 2-3)
Black resists 2 to 3 were prepared in the same manner as the black resist 1 of Example 1, except that the organosilicon compound 1 of Example 1 was changed to the organosilicon compound 2 and the organosilicon compound 3 described in Table 2-1.

<Examples 4-7 and 9-11>
(Preparation of black resists 4-7 and 9-11)
Black resists 4 to 7 and 9 to 11 were prepared in the same manner as the black resist 1 of Example 1, except that the photopolymerizable monomer DPHA of Example 1 was changed to the photopolymerizable monomers described in Tables 2-1 and 2-1. .

<Example 8>
(Preparation of black resist 8)
A black resist 8 was prepared in the same manner as the black resist 1 of Example 1, except that the content of the organosilicon compound 1 of Example 1 was changed from 0.5% by mass to 0.2% by mass.

<Comparative Example 1>
(Preparation of comparative black resist 1)
A comparative black resist 1 was prepared in the same manner as the black resist 1 of Example 1, except that no organosilicon compound was added in Example 1.

<Comparative Examples 2-4>
(Formulation of comparative black resists 2 to 4)
Comparative black resists 2 to 4 were prepared in the same manner as the black resist 1 of Example 1 except that the organosilicon compound of Example 1 was changed to a commercially available silane coupling agent described in Table 2-2.
In Comparative Examples 2 to 4, the following silane coupling agents were used.
SH6040: epoxy silane coupling agent (manufactured by Toray Industries, Inc.).
KBM-503: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
・ KBE-9007: 3-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Evaluation of resist)
(1) Production of black matrix (BM) The prepared black resists 1 to 11 and comparative black resists 1 to 4 were applied to a glass substrate with a spin coater, dried under reduced pressure, and then dried at 100 ° C. for 120 seconds with a hot plate. . Subsequently, the resulting dry coated film was subjected to pattern exposure through an exposure mask at 40 mJ with a high-pressure mercury lamp, and then alkali development adjusted to a 0.04 mass% KOH aqueous solution with ultrapure water at room temperature (23 ° C.). A resist pattern was obtained by spray development with a solution for 1.6 times the dissolution time. Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes to prepare a black matrix having a thickness of about 1 μm. The dissolution time is the time when the unexposed portion of the photosensitive layer is dissolved and the entire substrate begins to be visible during the current processing, and the dissolution time of each black resist and comparative black resist was 30 to 60 seconds.

(2) Light shielding degree: BM optical density (OD value) and evaluation of film thickness Using the prepared black resists 1 to 11 and comparative black resists 1 to 4, the film thickness of the BM produced in (1) is measured by a level difference measuring device. Measured by Alpha-Step-500 (KLA-Tencor), and OD value was measured by a transmission density measuring device GretagMacbeth D200-II (GretagMacbeth). From this, when the OD value per 1 μm (unit OD value) was determined, the BMs produced with the black resists 1 to 11 were all 4.2 / μm.

(3) Evaluation of substrate adhesion (high temperature and high humidity)
Substrate adhesion under high temperature and high humidity was evaluated using a black matrix prepared as follows using the prepared black resists 1 to 11 and comparative black resists 1 to 4.
Specifically, in “(1) Production of black matrix (BM)”, a 5 cm square of a black matrix having a thickness of 1.20 μm was obtained by the same process except that a mask was not used during exposure and development processing was not performed. A solid plate was formed. It was exposed for 2 hours in a steam atmosphere at 120 ° C., 2 atm, and relative humidity 100% (pressure cooker test, PCT). After that, the surface was cross-cut into a grid pattern, and cellophane tape (registered trademark CT-18S (18 mm width), manufactured by Nichiban Co., Ltd.) was peeled off by the method specified in JIS-K5600-5-6. The situation of peeling at the time was evaluated according to the following criteria.

(Substrate adhesion evaluation criteria)
A: No peeling at the substrate / BM interface due to tape peeling after PCT. No peeling of BM surface.
○: After PCT, peeling of the BM surface is observed minutely due to tape peeling, but there is no peeling at the substrate / BM interface.
(Triangle | delta): After PCT, the peeling in a board | substrate / BM interface is observed by tape peeling. Over 0% and within 10% of the evaluation area.
X: After PCT, peeling at the substrate / BM interface is observed by tape peeling. Over 10% and within 40% of the evaluation area.
XX: After PCT, peeling at the substrate / BM interface is observed by tape peeling. Over 40% and less than 100% of the evaluation area.
XXX: After PCT, peeling at the substrate / BM interface is observed on the entire substrate by tape peeling.

(4) Evaluation of substrate adhesion (room temperature)
The substrate adhesion at room temperature was evaluated with the black matrix produced as follows using the prepared black resists 1 to 11 and comparative black resists 1 to 4.
A 2.5 cm square solid plate of 1.20 μm thick black matrix in the same process except that the mask was not used at the time of exposure in “(1) Production of Black Matrix (BM)” and the development process was not performed. A sample for measurement was prepared by joining an aluminum stud pin (manufactured by Quad) using a sealant (manufactured by Mitsui Chemicals). The sample was subjected to a tensile test at a rate of 2.0 kg / s using Romulus (Quad), and the adhesion stress was calculated by the following formula from the breaking strength and adhesion area when the black matrix and the glass substrate were broken. Asked.
Adhesion stress (kg / cm ² ) = breaking strength (kg) / bonding area (cm ² )
The results are shown in Tables 2-1 and 2-2. In addition, the board | substrate adhesion force (%) in Tables 2-1 and 2-2 calculated | required the relative value (%) when the board | substrate adhesion force in the comparative example 1 was set to 100%.

(Substrate adhesion evaluation criteria)
3A: When the substrate adhesion strength of Comparative Example 1 is 100%, the substrate adhesion strength is 150% or more.
2A: When the substrate adhesion strength of Comparative Example 1 is 100%, the substrate adhesion strength is less than 150% to 120% or more.
1A: When the substrate adhesion strength of Comparative Example 1 is 100%, the substrate adhesion strength is less than 120% to 110% or more.
B: When the substrate adhesion strength of Comparative Example 1 is 100%, the substrate adhesion strength is less than 110%.

As shown in Tables 2-1 and 2-2, the photosensitive resin composition of the present invention contains the organosilicon compound (f-1), so that the BM, the substrate, and the substrate under high temperature and high humidity. The adhesion between the BM and the substrate was good even at room temperature.
The black resists 1, 2, and 3 of Examples 1, 2, and 3 are organosilicon compounds (f-1) that are a mixture of the silane monomer of the general formula (2) and the silane oligomer of the general formula (3). As described above, due to the synergistic effect of the silane site, urethane bond site, and ethylenically unsaturated group site in the structure, the adhesion between the substrate and BM under high temperature and high humidity becomes very good. It is considered that the adhesion between the substrate and the BM was good even at room temperature.

Examples 4-7 and 9-11 using not only the organosilicon compound (f-1) but also a polyfunctional (meth) acrylate monomer having a caprolactone structure as the photopolymerizable monomer (b) are esters thereof. The interaction between the polar groups of the bonding site and the urethane bonding site of the organosilicon compound (f-1) seems to facilitate the formation of a cross-linked structure, and the substrate adhesion effect under high temperature and high humidity is further improved. The effect of adhesion between the BM and the substrate was greatly improved.
On the other hand, not only the comparative black resist 1 of Comparative Example 1 containing no organosilicon compound (f), but also the comparative black resists 2 to 4 of Comparative Examples 2 to 4 are epoxy groups that contain other organosilicon compounds, (Meth) acryloyloxy group, only isocyanate group, can not obtain the synergistic effect due to urethane bonding site, high substrate adhesion at high temperature and high humidity and room temperature as seen in the examples There was no improvement.

Claims (15)

A photosensitive resin composition comprising an alkali-soluble resin (a), a photopolymerizable monomer (b), a photopolymerization initiator (c), a colorant (d), a dispersant (e) and an organosilicon compound (f). And
A photosensitive resin composition, wherein the organosilicon compound (f) contains at least an organosilicon compound (f-1) having a structure represented by the following general formula (1).

(In the above formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ^Ra is a group represented by the following formula (1-1). * Is a bond.)

(In the above formula, R ² and R ³ are each independently an alkylene group having 1 to 8 carbon atoms, R ⁴ is a hydrogen atom or a methyl group, and * is a bond with a Si atom.) The photosensitive resin composition according to claim 1, wherein the organosilicon compound (f-1) includes an organosilicon compound represented by the following general formula (2).

(In the above formula, R ¹ and R ^a have the same meaning as in the general formula (1). R ¹ contained in the formula may be the same or different.) The photosensitive resin composition according to claim 1, wherein the organosilicon compound (f-1) includes an organosilicon compound represented by the following general formula (3).

(In the above formula, R ¹ and R ^a have the same meaning as in the general formula (1). N represents an integer of 2 to 10. R ¹ and R ^a contained in the formula are the same as each other. Or different.) The photosensitivity according to any one of claims 1 to 3, wherein the photopolymerizable monomer (b) contains a compound represented by at least one of the following general formulas (b1) to (b4). Resin composition.

(In the above formula, R ^b is a group represented by the following formula (b5), and R ⁹ is an alkylene group having 1 to 10 carbon atoms, an arylene alkylene group having 7 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms. .)

(In the above formula, R ⁶ represents an alkylene group that may have 2 to 6 carbon atoms in the main chain, R ⁷ represents a hydrogen atom or a methyl group, and m represents an integer of 0 to 3. When m is 2 or 3, a plurality of R ⁶ may be the same or different.)   The photosensitive resin composition according to any one of claims 1 to 4, wherein the photopolymerization initiator (c) is an oxime ester.   The photosensitive resin composition according to claim 1, wherein the color material (d) is a black color material.   The photosensitive resin composition according to claim 1, wherein the content of the coloring material (d) is 40% by mass or more based on the total solid content.   The photosensitive resin composition according to any one of claims 1 to 7, wherein the dispersant (e) is a polymer dispersant having a basic functional group.   The photosensitive resin composition according to any one of claims 1 to 8, wherein the alkali-soluble resin (a) contains an ethylenically unsaturated group.   The photosensitive resin composition according to claim 9, wherein the alkali-soluble resin (a) contains an epoxy (meth) acrylate resin having a carboxyl group. The epoxy (meth) acrylate resin having a carboxyl group contains the following epoxy (meth) acrylate resin (A1-1) and / or the following epoxy (meth) acrylate resin (A1-2), Item 11. The photosensitive resin composition according to Item 10.
Epoxy (meth) acrylate resin (A1-1): An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to the epoxy resin, and a polybasic acid and Epoxy (meth) acrylate resin obtained by reacting an anhydride thereof / Epoxy (meth) acrylate resin (A1-2): α, β-unsaturated monocarboxylic acid or α having a carboxyl group on the epoxy resin , Β-unsaturated monocarboxylic acid ester, and epoxy (meth) acrylate resin obtained by reacting polyhydric alcohol with polybasic acid and / or anhydride thereof   Hardened | cured material formed by hardening the photosensitive resin composition of any one of Claims 1-11.   A black matrix comprising the cured product according to claim 12.   14. The black matrix according to claim 13, wherein the optical density per 1 [mu] m film thickness is 4.0 or more.   The image display apparatus produced using the black matrix of Claim 13 or 14.

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