JP6874805B2 - Photosensitive resin composition, cured product obtained by curing this, black matrix and image display device - Google Patents

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. More specifically, the present invention relates to a photosensitive resin composition having excellent adhesion to a substrate and its use.

An image display device such as a liquid crystal display (LCD) represented by a notebook computer or a liquid crystal television requires a color filter, a spacer, or the like having pixels and a black matrix (hereinafter, may be abbreviated as BM). A color filter is also required for colorizing a solid-state imaging device representing a charge-coupling element (CCD, CMOS) used as an input device of a digital camera, a color copy machine, or the like.

In the method of forming pixels by the pigment dispersion method, which is generally used at present, a photosensitive resin composition is first applied onto a substrate such as a glass substrate or a wafer, and then prebaked to form a film, and then a predetermined mask is formed. A colored cured film (colored pixel) is obtained by irradiating the irradiated portion with ultraviolet rays through the glass, curing the irradiated portion, removing the unirradiated portion by an alkali development treatment, and further performing heat treatment at a temperature of 200 ° C. or higher. This method applies the principle that a photopolymerization initiator generates an active radical by irradiation with ultraviolet rays, which attacks a photopolymerizable compound and induces a polymerization reaction. That is, the polymerization is initiated only when the active radical is present.

The photosensitive resin compositions used in these image display devices and solid-state image sensors are increasingly required to be miniaturized and thinned as the devices themselves become lighter, thinner, shorter, and smaller, and the resin components in the compositions are reduced. And the elimination of organic undercoats is being considered. In addition, high shading and high color density reproduction are also required, and the colorant density is becoming higher and higher. Therefore, the sensitivity is lowered and the adhesion to the substrate is lowered accordingly, and improvements are being made by various methods such as a photopolymerization initiator.

When the color material is irradiated with ultraviolet rays, the coexisting color material also absorbs the ultraviolet rays. Therefore, if the content of the color material is increased, the generation of active radicals is hindered, the curing becomes insufficient, and the adhesion to the substrate is lowered. On the other hand, if the amount of the photopolymerization initiator is increased in order to increase the generation of active radicals, the ultraviolet rays are absorbed by the surface layer initiator, and the ultraviolet rays do not reach the inside, so that the improvement of insufficient curing is not sufficient.

Furthermore, in recent years, in order to save energy, the market has been studying to make the line width of BM narrower and increase the brightness. Further, in order to reduce the manufacturing process at the time of producing a liquid crystal panel, studies have been made such as creating a conventional frame portion with BM, applying a sealant on the frame portion, and laminating a TFT substrate. In addition, BM substrate adhesion is required during increasing overseas transportation and in a high temperature and high humidity environment.

As the demand for substrate adhesion at room temperature, 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 a photosensitive resin composition has been studied. For example, in Patent Document 1, a silane coupling agent such as epoxy, (meth) acrylic, or vinyl is used to improve the adhesion of BM. It is stated that it will be improved. Further, Patent Document 2 describes that the development adhesion is improved by using a secondary, tertiary amine-based, ketimine-based, or isocyanate-based silane coupling agent.

Japanese Unexamined Patent Publication No. 10-133370 Japanese Unexamined Patent Publication No. 2008-129463

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

As a result of diligent research to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by containing a specific organosilicon compound in the photosensitive resin composition.
That is, the gist of the present invention is as follows.

[1] Photosensitive resin composition containing an alkali-soluble resin (a), a photopolymerizable monomer (b), a photopolymerization initiator (c), a coloring material (d), a dispersant (e), and an organosilicon compound (f). It ’s 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. R ^a is a group represented by the following formula (1-1). * Is a bonder.)

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

(In the above formula, R ¹ and ^Ra are synonymous with the general formula (1). A plurality of R ¹ included in the formula may be the same or different from each other.)
[3] The photosensitive resin composition according to [1] or [2], wherein the organosilicon compound (f-1) contains an organosilicon compound represented by the following general formula (3).

(In the above formula, R ¹ and ^Ra are synonymous with the general formula (1). In addition, n represents an integer of 2 to 10. R ¹ and R ^a included in a plurality of formulas are the same. It may be different.)
[4] Described in any one of [1] to [3], wherein the photopolymerizable monomer (b) contains a compound represented by at least one of the following general formulas (b1) to (b4). 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. Is.)

(In the above formula, R ⁶ represents an alkylene group in which the main chain may have branches of 2 to 6 carbon atoms, 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 ^6s 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 with respect to 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 is characterized by containing 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 polybasic acid and polybasic acid and / Or an epoxy (meth) acrylate resin obtained by reacting its anhydride. Epoxy (meth) acrylate resin (A1-2): An α, β-unsaturated monocarboxylic acid or α having a carboxyl group in the epoxy resin. , Β-Unsaturated monocarboxylic acid ester added, and further reacted with polyvalent alcohol with polybasic acid and / or its anhydride to obtain an epoxy (meth) acrylate resin.

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

According to the present invention, it is possible to provide a photosensitive resin composition having good substrate adhesion at room temperature and high temperature and high humidity in the case of high colorant concentration or high miniaturization.

It is sectional drawing which shows an example of the organic EL element provided with the color filter of this invention.

Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.
In the present invention, "(meth) acrylic" means "acrylic and / or methacrylic", and the same applies to "(meth) acrylate" and "(meth) acryloyl".

In the present invention, the "total solid content" means all the components other than the solvent contained in the photosensitive resin composition or the ink described later.
In the present invention, the weight average molecular weight refers to the polystyrene-equivalent weight average molecular weight (Mw) obtained by GPC (gel permeation chromatography).
Further, in the present invention, the "amine value" represents an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the amount of base per 1 g of solid content of the dispersant and the weight of equivalent KOH. Is. The measurement 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 coloring material (d), a dispersant (e), and an organosilicon compound (f). ), The organosilicon compound (f) is characterized by containing the organosilicon compound (f-1) having a structure represented by the following 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 independently alkylene groups 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, further an adhesion improver, a coatability improver, a development improver, and ultraviolet absorption. 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 of being dissolved or dispersed in an organic solvent.
One of the features of the present invention is that the photosensitive resin composition contains an organosilicon compound (f). First, the organosilicon compound (f) will be described.

<Organosilicon 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 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 independently alkylene groups 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.
For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopentyl group, a cyclohexyl group and the like can be mentioned. 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.

Further, 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, a methylene group, an ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 1,4-butylene group, or a 1,2-butylene group is preferable from the viewpoint of ease of handling and reactivity. Ethylene groups, 1,3-propylene groups, or 1,2-propylene groups are more preferred.

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

In the above formula, R ¹ and ^Ra have the same meaning as the general formula (1). R ¹ together contained more in the formula can be different even in respectively the same.

The monomer of the general formula (2) itself has the structure of the general formula (1), but oligomers of the monomers and oligomers of the monomer and an organosilicon compound having another structure are also available. , The structure of the general formula (1) can be obtained.

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: An organosilicon compound containing an oligomer of the monomers of the general formula (2).
Embodiment 3: An organosilicon compound containing an oligomer of the monomer of the general formula (2) and a monomer other than the general formula (2).
Embodiment 4: An organosilicon compound containing an oligomer of the oligomer of the second embodiment and a monomer other than the general formula (2).

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

In the above formula, R ¹ and ^Ra have the same meaning as the general formula (1). R ¹ together contained more in the formula can be different even in respectively the same.

The monomer represented by the general formula (2) comprises an organic silane 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 is carried out 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 are synonymous with 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 are synonymous with the above general formula (1-1).)

Examples of the catalyst in this reaction include organotin compounds such as dibutyltin maleate, tributyltin acetate, dimethyltin dichloride, dibutyltin diacetate, and dibutyltin dilaurate; N-methylmorpholine, triethylamine, N-methylpiperidin, N, N-dimethyl. Tertiary amines such as cyclohexylamine and pyridine are useful, and the amount added thereof is 0.001 to 1% by mass, particularly 0.01 to 0.% With respect to the silane compound of the general formula (2-1). 1% by mass is preferable. The reaction temperature is preferably 0 to 50 ° C, more preferably 20 to 40 ° C. The reaction time can be appropriately selected from 1 to 24 hours. The above reaction is usually solvent-free, but if necessary, an organic solvent such as hexane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran, or acetonitrile may be used.

Specific examples of the monomer represented by the general formula (2) include the following, but the monomer is not particularly limited as long as it satisfies the general formula (2).

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

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

In the above formula, R ¹ and ^Ra have the same meaning as the general formula (1). Further, n represents an integer of 2 to 10. R ¹ and R ^a together contained more in the formula can be different even in respectively the same.

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) can be obtained by oligomerizing the monomer represented by the general formula (2) described in the first embodiment by a general method such as hydrolysis or heating. .. Details will be described later.

The organosilicon compound (f-1) in the second embodiment may contain not only the oligomer represented by the general formula (3) but also the monomer represented by the general formula (2). Further, the organosilicon non-compound (f) in the second embodiment contains a monomer other than the general formula (2) and an oligomer other than the general formula (3) as long as the effect of the present invention is not affected. It may be included.
The organosilicon compound (f-1) in the second embodiment preferably contains both the monomer represented by the general formula (2) and the oligomer represented by the general formula (3). The reason is that the monomer alone may volatilize and decrease due to the high temperature treatment at the time of making the color filter, but with the oligomer alone, the oligomers are further hydrolyzed by the high temperature treatment to become a multimer, and the molecular weight is large. This is because it tends to remain as a residue on the substrate during alkaline development.

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

The organosilicon compound (f) of the second embodiment may contain other monomers or oligomers as long as it does not affect the adhesion effect.

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

When the organosilicon compound (f-1) contains both the monomer represented by the general formula (2) and the oligomer represented by the general formula (3), it is relative to the organosilicon compound (f). 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, still more preferably. Is 65 mol% or more, particularly preferably 80 mol% or more, and usually 100 mol% or less. By setting the value to the lower limit or more, there is a tendency that the adhesion to the substrate can be improved.
The ratio of the content mass of the oligomer represented by the general formula (3) to the monomer represented by the general formula (2) is the content mass of the monomer represented by the general formula (2). : The content mass of the oligomer represented by the general formula (3) is preferably in the range of 0.1: 99.9 to 99.9: 0.1. Within the above range, the adhesion to the substrate tends to be improved.

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 more preferably 2000 or less. Especially preferable. By setting the value to the upper limit or less, there is a tendency that the residue on the substrate during alkaline development can be improved.

The method for obtaining the oligomer represented by the general formula (3) is not particularly limited, but it can be obtained, for example, by hydrolyzing the monomer represented by the general formula (2). Specifically, the monomer is put into a solvent such as alcohol or propylene glycol methyl ether acetate that can be easily distilled and removed later, and a small amount of acid such as oxalic acid is added as a catalyst, or ionized water is added. Oligomers can be obtained by heating at 50 to 150 ° C. for 1 to 12 hours. These hydrolysis reactions are carried out by generally known methods, for example, the methods described in paragraphs [0998] to [0099] of JP2012-27480A and the methods described in synthetic examples. Can be obtained.

<Organosilicon compound of Embodiment 3>
The organosilicon compound (f-1) of the third embodiment is an oligomer of a monomer represented by the general formula (2) and a monomer other than the general formula (2) (hereinafter, “copolymerization oligomer””. It is an organosilicon compound containing (may be abbreviated as).

As the organosilicon compound (f-1) of the third embodiment, for example, a monomer represented by the general formula (2) and a monomer other than the general formula (2) are described in the second embodiment. It is obtained by a method of oligomerizing by such a hydrolysis reaction.

By introducing a structure derived from a monomer other than the general formula (2) in addition to the structure derived from the monomer represented by the general formula (2), the photosensitivity is exhibited. The interaction and compatibility with the alkali-soluble resin, photopolymerizable monomer, photopolymerization initiator, coloring material, dispersant, etc. in the sex resin composition can be adjusted, and the effect 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 forming property can be obtained. In particular, there is a tendency that the alkali development residue can be improved by introducing a structure derived from the monomer using a monomer having a hydroxyl group or a carboxyl group having good alkali developability.

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 and tertiary amino group, and ureido group. , Those having a mercapto group, an isocyanate group and the like.

In addition, a single amount having an epoxy group, an oxetanyl group, an episulfide group, a vinyl group, an allyl group, a (meth) acryloyl group, a carboxyl group, a hydroxyl group, a mercapto group, an isocyanate group, an amino group, a ureido group and a styryl group. Specific examples of the body are described in paragraphs [2002] to [0995] of JP2012-27480A, and these can also be used as the monomer of the third embodiment.
Further, the monomers described in paragraphs [0996] to [097] in the same publication may also be used as the monomers of the third embodiment as long as the effects of the present invention are not affected.
Further, a monomer other than the above can also be used as the monomer of the third embodiment as long as the effect of the present invention is not affected.

Further, the organosilicon compound (f-1) of the third embodiment may contain an oligomer represented by the general formula (3), or a monomer represented by the general formula (2). It may be included. Further, the organosilicon compound (f) may contain other silane monomers to the extent that it does not affect the adhesion effect of the present invention.

In the third embodiment, the content ratio of the copolymerized 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 mol% or more, and usually 100 mol% or less. By setting the value to the lower limit or more, there is a tendency that the adhesion to the substrate can be improved.
The content ratio of the copolymerized oligomer 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, and also. Usually 100 mol% or less. By setting the value to the lower limit or more, there is a tendency that the adhesion to the substrate can be improved.

The weight average molecular weight of the copolymerization oligomer of the third embodiment is preferably 30,000 or less, more preferably 10,000 or less, and even more preferably 5,000 or less. By setting the value to the upper limit or less, it tends to be possible to prevent the residue from remaining on the substrate during alkaline development.

<Organosilicon compound of embodiment 4>
The organosilicon compound (f-1) of the fourth embodiment is abbreviated as an oligomer (hereinafter, abbreviated as "block oligomer") of an oligomer represented by the general formula (3) and a monomer other than the general formula (2). It is an organosilicon compound containing (may be).

The organosilicon compound (f-1) of the fourth embodiment is, 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 oligomerizing by a hydrolysis reaction.

Embodiment 3 by introducing a structure derived from a monomer other than the general formula (2) in addition to the structure derived from the oligomer represented by the general formula (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 can be obtained. In particular, there is a tendency that the alkali development residue can be improved by introducing a structure derived from the monomer using a monomer having a hydroxyl group or a carboxyl group having good alkali developability.

As the monomer other than the general formula (2), the monomer described in the third embodiment can be applied.

Further, the organosilicon compound (f-1) of the fourth embodiment may contain the copolymerization oligomer, may contain an oligomer represented by the general formula (3), or may contain the oligomer represented by the general formula (3). It may contain the monomer represented by (2). Further, the organosilicon compound (f) may contain other silane monomers and the like to the extent that it does not affect the adhesion effect of the present invention.

In the fourth embodiment, the content ratio of the block 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 mol%. % Or more, and usually 100 mol% or less. By setting the value to the lower limit or more, there is a tendency that the adhesion to the substrate can be improved.
The content ratio of the block oligomer 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, and usually. It is 100 mol% or less. By setting the value to the lower limit or more, there is a tendency that the adhesion to the substrate can be improved.

The weight average molecular weight of the block oligomer of the fourth embodiment is preferably 20000 or less, more preferably 8000 or less, and further preferably 4000 or less. By setting the value to the upper limit or less, it tends to be possible to prevent the residue from remaining on the substrate during alkaline development.

Further, in the first to fourth embodiments, the content ratio of the organosilicon compound (f) in the photosensitive resin composition is preferably 0.01% by mass or more, preferably 0.1% by mass or more, based on the total solid content. It is more 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 it is set to the lower limit value or more, the adhesion to the substrate tends to be good, and when it is set to the upper limit value or less, the residue tends to be suppressed from remaining on the substrate during alkaline development.

Although the first to fourth embodiments have been described in detail above, as the organosilicon compound (f-1), the organosilicon compound (f-1) of the first embodiment or the second embodiment is preferable, and the general formula (3) is particularly preferable. ) And the monomer represented by the general formula (2) are preferably mixed.

<Multifunctionalization of ethylenically unsaturated groups having the structure of equation (1)>
The ethylenically unsaturated group in the general formula (1-1) can also be polyfunctionalized as follows. Examples of the method for obtaining the polyfunctionalized organosilicon compound (f-1) include a method using a monomer in which the ethylenically unsaturated group is polyfunctionalized in the monomer of the general formula (2). Be done. Specifically, it can be obtained by the same method as in the first embodiment by using the 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 are synonymous with the general formulas (1) and (1-1).)
XY- (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 is synonymous with the general formula (1-1). .M is an integer of 2-6).

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

As another method of polyfunctionalization, for example, in the monomer of the general formula (2), the active hydrogen on the 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 conducting 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 a structure represented by the general formula (1), but is represented by the general formula (1). It may contain other organosilicon compounds that do not have the structure to be used. For example, a monomer represented by the following formula (4) or (5), which is similar to the general formula (2), can be mentioned.

In the above formula, R ^{1 to} R ⁴ are synonymous with the above formula (2). In addition, R ^α represents an −S— group or an −NH− group.

In the above formula, R ^{1 to} R ⁴ are synonymous with the above formula (2). In addition, R ^β represents an —O— group, an —S— group or an −NH— group.

The silane monomer represented by the general formula (4) includes an isocyanate-containing silane compound represented by the following general formula (4-1) and the following general formula (4-2) or (4-3). It can be synthesized by subjecting the (meth) acryloyloxy compound represented by (meth) to 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 are synonymous with the above 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 are synonymous with the above 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). )-(5-4) is synthesized by subjecting to a urethane reaction, a thiourethane reaction, or a urea reaction in the presence of a catalyst as in the known method described in the first embodiment. Can be done.
CH ₂ = CR ^4- CO-O-R ^3- N = C = O (5-1)
(In the above formula, R ³ and R ⁴ are synonymous with the above 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 are synonymous with the above general formula (5))

Among these, the silane monomer represented by the general formula (4) is preferable.
The reason is that these functional groups in the (meth) acryloyloxy compound containing functional groups such as thiol group, primary amino group and secondary amino group that react with isocyanate are the isocyanate of the silane compound having an isocyanate group. Urethane bonds are easily formed selectively by reaction with groups, reaction with unsaturated groups in (meth) acryloyloxy groups is unlikely to occur, and synthesis is easy, and this structure is effective for improving adhesion. Things can be mentioned. Further, when these functional groups of the (meth) acryloyloxy compound having a functional group such as a thiol group, a primary amino group, or a secondary amino group that reacts 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 during alkaline development during production, and that the urethane bonding portion in the general formula (4) works 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 in which a plurality of types of monomers are mixed. Further, these monomers may be hydrolyzed to obtain an oligomer, which may be used. These may be mixed with other alkoxysilane monomers and oligomers. Further, the monomer of the general formula (4) or (5) and other alkoxysilane monomer may be hydrolyzed to obtain an oligomer, which may be used.

The silane monomer of the general formula (4) or (5) may also be used in the same manner as in Embodiments 2, 3 and 4.

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

First, by having a silane moiety, the silanol group is adsorbed by the interaction between the polar group of the substrate and hydrogen bonds, and the alkoxy group also becomes a silanol group by hydrolysis due to the action of water under high humidity. It is considered that the adhesion with the substrate is improved by the same adsorption. In particular, when the substrate is a glass substrate, it is considered that a hydrogen bond is formed with a silanol group on the surface of the glass substrate, and 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 treated under high humidity and high temperature conditions during the coating drying treatment, the alkaline developer treatment, or the high temperature heat treatment of 200 ° C. or higher, or when the color filter is manufactured. It is also formed later during overseas transportation and use under high humidity and high temperature.

Further, the urethane bond site in the general formula (1-1) includes a carboxyl group, an ester group, an epoxy acrylate group and the like contained in an alkali-soluble resin, a photopolymerizable monomer, a dispersant and the like in the photosensitive resin composition. It is considered that the photosensitive resin composition and the substrate are more firmly adhered to each other via the organic silicon compound (f-1) by forming a bond with the polar group by hydrogen bonding or charge interaction.
In particular, when the photopolymerizable monomer has an ester bond or the dispersant has a urethane bond, this effect is synergistically improved.

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

As described above, due to the synergistic effect of the silane site in the general formula (1), the urethane binding site in the general formula (1-1), and the unsaturated group site, the substrate and the photosensitive resin composition are combined. It is considered that the adhesion is greatly improved.

<Substrate adhesion effect at room temperature>
The structure of the general formula (1) has an effect of improving the adhesion between the substrate and the cured film even at room temperature, and the action is considered to be as follows.

The effect of having a silane moiety on the substrate surface tends to be not as great as the effect under high temperature and high humidity, but it is treated with water contained in the photosensitive resin composition or an alkaline developing aqueous solution. Moisture that is sometimes taken into the surface of the substrate or the photosensitive layer is subsequently post-baked at a high temperature of 200 ° C. or higher, so that it is hydrolyzed and the adhesion to the substrate is improved. Further, due to the synergistic effect of the urethane binding 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 the present invention contains an alkali-soluble resin (a). The alkali-soluble resin (a) is coated with a photosensitive resin composition containing the photopolymerizable monomer (b), a photopolymerization initiator (c), a coloring material (d) and an organic silicon compound (f), and dried. The cured film thus obtained is not particularly limited as long as the solubility of the exposed portion and the non-exposed portion in alkali development changes after exposure, but an alkali-soluble resin having a carboxyl group is preferable. Further, those having an ethylenically unsaturated group are preferable, and an alkali-soluble resin having an ethylenically unsaturated group and a carboxyl group is more preferable. Specific examples thereof include epoxy (meth) acrylate resins and acrylic copolymer resins having a carboxyl group, and more specific examples thereof are described below (A1-1), (A1-2), and (A2-). Examples thereof include those described as 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 applied as the polymer resin in order to dissolve the non-exposed portion in the alkaline developer. To. Among these, a polymer resin having a carboxyl group is preferable from the viewpoint of solubility in an alkaline developer. Further, although the phosphoric acid group and the sulfonic acid group have higher acidity than the carboxyl group, they easily react with the initiator, monomer, dispersant, and other additives having a basic group in the photosensitive resin composition. , Storage stability may deteriorate.

Further, 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-like interaction. This tends to further improve the adhesion between the photosensitive resin composition and the substrate.

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

Further, when an epoxy acrylate resin is used as an alkali-soluble resin having a carboxyl group and an ethylenically unsaturated group, more unsaturated bonds and carboxyl groups can be added in the resin, and an aromatic ring can be added. It is possible to include a large amount of structure or a three-dimensionally bulky alicyclic structure, further increase the interaction with the organic silicon compound (f-1), and improve the adhesion to the substrate. It tends to improve further.

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 α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting with a polybasic acid and / or its anhydride. 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 the epoxy resin, and the epoxy resin is further reacted with a polyhydric alcohol and a polybasic acid and / or its anhydride. The alkali-soluble resin obtained by this.

(Epoxy (meth) acrylate resin (A1-1) having a carboxyl group and an ethylenically unsaturated group bond)
Examples of the epoxy resin used as a raw material include 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 the reaction of the alcoholic hydroxyl group of the bisphenol A type epoxy resin with epichlorohydrin (for example, "NER-1302" (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin ( For example, "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 a bisphenol F type epoxy resin with epichlorohydrin. (For example, "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66 ° C.)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), Phenol novolac type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Co., Ltd.), ( o, m, p-) Cresol novolac type epoxy resin (for example, "EOCN (registered trademark; the same applies hereinafter) -102S", "EOCN-1020", "EOCN-104S") manufactured by Nippon Kayakusha Co., Ltd., triglycidyl Isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Corporation), trisphenol methane type epoxy resin (for example, "EPPN (registered trademark; the same applies hereinafter) -501" manufactured by Nippon Kayaku Co., Ltd.), "EPN" -502 "," EPPN-503 "), alicyclic epoxy resin ("Ceroxide (registered trademark; the same shall apply hereinafter) 2021P "manufactured by Daicel Chemical Industries, Ltd.," Celoxide EHPE "), by the reaction of dicyclopentadiene and phenol. Epoxy resin obtained by glycidylating a phenol resin (for example, "EXA-7200" manufactured by Dainippon Ink Co., Ltd., "NC-7300" manufactured by Nihon Kayaku Co., Ltd.), represented by the following general formulas (a1) to (a4). Epoxy resin, etc. can be preferably used. Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (a1), and "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (a2). Examples of the epoxy resin represented by the following general formula (a4) include "NC-3000" and "ESF-300" manufactured by Nippon Steel Chemical Co., Ltd.

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

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

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

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

In the above general formula (a4), p and q each independently represent an integer of 0 to 4, and R ⁴¹ and R ⁴² independently represent an alkyl group or a halogen atom, respectively. R ⁴³ and R ⁴⁴ each independently represent an alkylene group. x and y each independently represent an integer of 0 or more.
Among these, it is preferable to use the epoxy resin represented by any 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, and (meth). ) Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, cyano-substituted acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( Meta) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2-( Meta) acryloyloxypropyl adipinic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) ) Acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutyl hydrophthalic acid, 2- (meth) acryloyloxybutyl phthalic acid, 2- (meth) Acryloyloxybutylmaleic acid,
The (meth) acrylic acid ester is a single amount having one hydroxyl group at the end by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to (meth) acrylic acid. Body and
Alternatively, a monomer having one hydroxyl group at the terminal such as hydroxyalkyl (meth) acrylate, or a compound having 11 hydroxyl groups at the terminal such as pentaerythritol tri (meth) acrylate, and (maleic anhydride) succinic acid, Examples thereof include (meth) acrylic acid esters having one or more ethylene unsaturated groups and one carboxyl group at the end by adding an acid (anhydrous) such as (anhydrous) phthalic acid and (maleic anhydride) maleic acid. .. In addition, (meth) acrylic acid dimer and the like can also be mentioned.

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

As the epoxy resin, α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst, one type may be used alone or two types may be used. The above may be used together.
The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin. , More preferably in the range of 0.7 to 1.1 equivalents.
If the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group used is small, the amount of unsaturated group introduced will be insufficient, and the subsequent polybasic acid and / or its anhydride will be insufficient. The reaction with is also insufficient. It is also 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, the curing characteristics tend to deteriorate.

Polybasic acid and / or its anhydride includes maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid. Examples thereof include one or more selected from acids, endomethylene tetrahydrophthalic acid, chlorendic acid, methyl tetrahydrophthalic acid, biphenyl tetracarboxylic acid, and anhydrides thereof.

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

A known method can also be used for the addition reaction of polybasic acid and / or its anhydride, and α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid having a carboxyl group to an epoxy resin can be used. The desired product can be obtained by continuing the reaction under the same conditions as the addition reaction of the ester. The amount of the polybasic acid and / or its anhydride component added is preferably such that the acid value of the produced carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mgKOH / g, and further 20 It is preferably in the range of ~ 140 mgKOH / g. If 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 if it exceeds the above range, the curing performance tends to be poor.

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

As the carboxyl group-containing epoxy (meth) acrylate resin, one type may be used alone, or two or more types of resins may be mixed and used.
If the amount of polyhydric alcohol used is too small, the effect will be weak, and if it is too large, thickening or gelation may occur. Therefore, a carboxyl group is added to the epoxy resin component and the α, β-unsaturated monocarboxylic acid or ester moiety. It is usually about 0.01 to 0.5 times by mass, preferably about 0.02 to 0.2 times by mass with respect to the reaction product with the α, β-unsaturated monocarboxylic acid ester component.

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, the developability may be insufficient. Further, if the acid value is excessively high, there may be a problem in the alkali resistance of the photosensitive assembly resin product (that is, the alkaline developer causes roughening of the pattern surface and film loss), so that the acid value may occur. Is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.

The polystyrene-equivalent weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (A1-1, A1-2) measured by gel permeation chromatography (GPC) is preferably 1,000 or more, preferably 1,500. The above is more preferable. Further, it is preferably 10,000 or less, more preferably 8,000 or less, and further preferably 6,000 or less. If the weight average molecular weight is too small, problems may occur in sensitivity, coating film strength, and alkali resistance, and if it is too large, problems may occur in developability and resolubility.

(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. , JP-A-2003-233179, JP-A-2007-270147, and the like, and various polymer compounds described in each publication can be used, but the following (A2-1) to (A2-) are preferable. Examples thereof include the resin of 4), and among them, the resin of (A2-1) is particularly preferable.

(A2-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. The resin to be added, or the resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction (hereinafter, may be referred to as "(A2-1) resin").
(A2-2): A linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter, may be referred to as "(A2-2) resin").
(A2-3): A 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): (Meta) acrylic resin (hereinafter sometimes referred to as "(A2-4) resin")
The above 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 radically polymerizable monomer, unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Resin to be added, or resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction>
More specifically, the resin (A2-1) is based on "a copolymer of 5 to 90 mol% of an epoxy group-containing (meth) acrylate and 10 to 95 mol% of another radically polymerizable monomer. , A resin made 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 the hydroxyl groups generated by the addition reaction. "Resin obtained by adding".

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

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

In the above general formula (11), R ^{81 to} R ⁸⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, but R ⁸⁷ and R ⁸⁸ are linked to each other to form a ring. You may.
In the above 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 preferable.

Among them, as the structure represented by the general formula (11), the structure represented by the following formulas (11a), (11b), or (11c) is preferable.

By introducing these structures into an alkali-soluble resin, the heat resistance and strength of the photosensitive resin composition of the present invention can be enhanced when it is used in a color filter or an image display device.
As the mono (meth) acrylate having the structure represented by the general formula (11), various acrylates can be used as long as they have the structure, but 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 radically polymerizable monomer, the repeating unit derived from the mono (meth) acrylate having the structure represented by the general formula (11) is Among the repeating units derived from "other radically polymerizable monomers", those containing 5 to 90 mol% are preferable, and those containing 15 to 50 mol% are particularly preferable.

The "other radically polymerizable monomer" other than the mono (meth) acrylate having the structure represented by the general formula (11) is not particularly limited.
The copolymer of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer of the resin (A2-1) is a repeating unit of 5 to 90 mol derived from the epoxy group-containing (meth) acrylate. % And 10 to 95 mol% of repeating units derived from other radically polymerizable monomers are preferable, and 30 to 70 mol% of the former and 70 to 30 mol% of the latter are particularly preferable.

In the (A2-1) resin, an unsaturated monobasic acid (polymerizable component) is added to the epoxy group portion of the copolymer of the above epoxy resin-containing (meth) acrylate and another radically polymerizable monomer. React with polybasic acid anhydride.
As the "unsaturated monobasic acid" to be added to the epoxy group, various substances 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, in which the α-position is substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, a cyano group, or the like. Examples thereof include monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferable. These may be used alone or in combination of two or more.

By adding such a component, the (A2-1) resin can be imparted with polymerizable properties.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy groups of the copolymer, but preferably to 50 to 100 mol%.
Further, various "polybasic acid anhydrides" can be used as the "polybasic acid anhydride" to be added to the hydroxyl group generated when the 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 acids having three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and succinic anhydride are preferable. One of these polybasic acid anhydrides may be used alone, or two or more thereof may be used in combination.

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 groups generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 30 to 80 mol. Add to%.

<(A2-2) Linear alkali-soluble resin containing a carboxyl group in the main chain>
The resin (A2-2) 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, phthalic acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl adipic acid. , 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl succinic acid, 2-( Meta) acryloyloxypropyl adipate, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxybutyl Vinyls such as succinic acid, 2- (meth) acryloyloxybutyl adipate, 2- (meth) acryloyloxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid System monomer: Acryloyl to which lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone are added; hydroxyalkyl (meth) acrylate with succinic acid, maleic acid, Examples thereof include phthalic acid, and monomers to which an acid such as an anhydride thereof or an anhydride is added. These may be used alone or in combination of two or more.

Of these, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is more preferable.
Further, the resin (A2-2) may be obtained by copolymerizing the above-mentioned 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. Further, among these polymerizable monomers, a copolymer resin containing benzyl (meth) acrylate is particularly preferable from the viewpoint of excellent pigment dispersibility.

<(A2-3) Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the (2-2) resin>
In the (A2-3) resin, the epoxy group-containing unsaturated compound 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. It is not something that is done.

Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, glycidyl ether (iso) crotonate, and N- (3,5-dimethyl). Acyclic epoxy group-containing unsaturated compounds such as -4-glycidyl) benzylacrylamide and 4-hydroxybutyl (meth) acrylate glycidyl ether can be mentioned, but from the viewpoint of heat resistance and dispersibility of the pigment, they are described below. 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] Desi-2-yl] group and the like. The ethylenically unsaturated group is preferably derived from a (meth) acryloyl group.

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

In the above general formula (6), R ⁷¹ and R ⁷² each independently represent a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.
Hereinafter, the compound of the general formula (6) will be described in 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, but for example.} , Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl and other linear or branched alkyl groups; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; alkoxy groups such as 1-methoxyethyl and 1-ethoxyethyl. Substituent alkyl groups; examples include alkyl groups substituted with aryl groups such as benzyl. Among these, a substituent having a primary or secondary carbon atom which is difficult to be eliminated by an acid or heat such as methyl, ethyl, cyclohexyl, and benzyl is particularly preferable in terms of heat resistance. In addition, R ⁷¹ and R ⁷² may be the same type of substituents 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 and 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 proportion of the ether dimer in the monomer component when the resin (A2-4) is obtained is not particularly limited, but is usually 2 to 60% by mass, preferably 5 to 50% by mass in the total monomer component.
The (A2-4) resin preferably has an acid group. By having an acid group, the photosensitive resin composition of the present invention obtained by using the acid group has a cross-linking reaction in which the acid group and the epoxy group react to form an ester bond (hereinafter, abbreviated as "acid-epoxy curing"). A photosensitive resin composition that can be cured by (), or a photosensitive resin composition that can visualize the uncured portion with an epoxy developing solution. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic acid anhydride group. These acid groups contained in one molecule of the resin may be only one kind or two or more kinds.

(A2-4) In order to introduce an acid group into a resin, for example, a monomer having an acid group and / or a "monomer capable of imparting an acid group after polymerization" (hereinafter, "a monomer for introducing an acid group"). (Sometimes referred to as) may be used as a monomer component. When a "monomer capable of imparting an acid group after polymerization" is used as a monomer component, a treatment for imparting an acid group as described later is required after the polymerization.

Examples of the monomer having an acid group include a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid; a monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; and maleic anhydride, itaconic anhydride and the like. Monomers having a carboxylic acid anhydride group and the like can be mentioned, and among these, (meth) acrylic acid is particularly preferable.
Examples of the monomer capable of imparting an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; a monomer having an epoxy group such as glycidyl (meth) acrylate; and 2-isocyanate ethyl (meth). ) Monomers having an isocyanate group such as acrylate can be mentioned.

As the monomer for introducing these acid groups, one type may be used alone, or two or more types may be used in combination. (A2-4) When the monomer component for obtaining the resin also contains the monomer for introducing the acid group, the content ratio thereof is usually 5 to 70% by mass, preferably 10 to 60% by mass in the total monomer components. It is mass%.
(A2-4) In addition to the above-mentioned essential monomer components, the monomer component for obtaining the resin may contain other copolymerizable monomers, if necessary.

As described above, the photosensitive resin composition of the present invention contains (A1-1), (A1-2), (A2-1), (A2-2), (A2-3), and (A2) as alkali-soluble resins. It is preferable to include at least one of -4).
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 it. The photosensitive resin composition of the present invention particularly preferably contains at least one of (A1-1) and (A1-2), which is an epoxy acrylate resin, 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.
The other alkali-soluble resins are not limited, and may be selected from the resins usually used in the photosensitive resin composition for color filters. For example, the alkali-soluble resins described in JP-A-2007-217727, JP-A-2007-316620, JP-A-2007-334290 and the like can be mentioned.

The content of the alkali-soluble resin (a) is usually 5% by mass or more, preferably 10% by mass or more, and usually 85% by mass or less, preferably 85% by mass or less, based on the total solid content of the photosensitive resin composition of the present invention. It is 80% by mass or less. When the content of the alkali-soluble resin (a) is extremely small, the solubility of the unexposed portion in the developing solution is lowered, and there is a tendency that development defects are easily induced. On the contrary, if the content of the alkali-soluble resin (a) is too large, the permeability of the developing solution to the exposed portion tends to be high, and the sharpness and adhesion of the pixels may be lowered.
As described above, the photosensitive resin composition of the present invention contains the above-mentioned (A1-1), (A1-2), (A2-1), and (A2-2) as the alkali-soluble resin (a). , (A2-3) and (A2-4) are preferably contained, and when other alkali-soluble resins are contained, the content ratio thereof is 20% by mass with respect to the total of the alkali-soluble resins (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), epoxy acrylate resins having an ethylenically unsaturated group (A1-1) and (A1-2) are particularly preferable. The resin may be used alone or in combination of two or more.

<Photopolymerizable monomer (b)>
The photosensitive resin composition of the present invention contains a photopolymerizable monomer (b) from the viewpoint of sensitivity and the like.
Examples of the photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter, may be referred to as “ethyleney monomer”). Specifically, for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, and a monoester of a 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, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, an aromatic. Examples thereof include an ester 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, trimethyl propantriacrylate, trimethylol ethanetriacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, and methacrylic acid esters in which the acrylates of these exemplified compounds are replaced with methacrylates. Similarly, an itaconic acid ester in place of itaconate, a crotonic acid ester in place of clonate, a maleic acid ester in place of maleate, and the like can be mentioned.

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

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

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 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 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 from 0 to 3. When m is 2 or 3, the plurality of R ^6s may be the same or different.

^{R 8} in the general formula (b3) is an alkyl group having 1 to 6 carbon atoms, but the carbon number is usually 1 or more, preferably 2 or more, and preferably 5 from the viewpoint of adhesion to the substrate. Hereinafter, it is more preferably 4 or less. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, a 2-butyl group, a 1-pentyl group, a 1-hexyl group and a cyclohexyl. Examples thereof include groups, and 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 of R 9} is usually 1 or more, preferably 2 or more, preferably 6 or less, and 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 a methylene group, an ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 1,4-butylene group, a 1,2-butylene group, and 1,5. -Pentylene group, 1,6-hexylene group, cyclohexylene group, methylenecyclohexylene group and the like can be mentioned. Among these, methylene group, ethylene group or 1,3- is preferable from the viewpoint of adhesion to the substrate. It is a propylene group, more preferably an ethylene group.
In the general formula (b4), ^{the arylene alkylene group of R 9} has preferably 7 or more carbon atoms and preferably 9 or less carbon atoms from the viewpoint of adhesion to the substrate. Examples of the arylene alkylene group having 7 to 10 carbon atoms include a phenylene methylene group, a phenylene ethylene group, and a phenylene propylene group. Among these, a phenylene methylene group or a phenylene methylene group is preferable from the viewpoint of adhesion to a substrate. It is a phenylene ethylene group, more preferably a phenylene methylene group.
In the general formula (b4), ^{the carbon number 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, and 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 in which the main chain may have branches having 2 to 6 carbon atoms, but the carbon number is preferably 3 or more from the viewpoint of adhesion to the substrate. 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 preferable that the alkylene group does not have a branch from the viewpoint of adhesion to the substrate. Examples of the alkylene group which may have a branch having 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 and a 1,4-butylene group. Examples thereof 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 and cyclohexylene group. Among these, from the viewpoint of adhesion to the substrate, a 1,4-butylene group or a 1,5-pentylene group is preferable, and a 1,5-pentylene group is more preferable.

m represents an integer from 0 to 3. Although in the above general formula (b1) ~ (b4) includes plurality of R ^b group, R ^b groups together may be different even in the same. From the viewpoint of adhesion to the substrate, ^{it is preferable that R bs} are different from each other, and it is more preferable that they have ^{R b groups having different m. 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) are combined. It is preferable to have. The m in the R ^b2 group is preferably 1 or 2 from the viewpoint of adhesion to the substrate, and more preferably 1.

^{Of the plurality of R b} groups contained in the general formula (b1), at least one ^{is preferably R b2} groups, and at least two are more preferably ^{R b2 groups.
Of the plurality of R b} groups contained in the general formula (b2), at least one ^{is preferably R b2} groups, and at least two are more preferably ^{R b2 groups.
Of the plurality of R b} groups contained in the general formula (b3), at least one ^{is preferably R b2} groups, and at least two are more preferably ^{R b2 groups.
Of the plurality of R b} groups contained in the general formula (b4), at least one ^{is preferably R b2} group, and at least two are more preferably ^{R b2 group.}

The reason why it is preferable that the photopolymerizable monomer (b) contains such a specific compound in the photosensitive resin composition of the present invention is as follows.
It is considered that such a specific compound interacts with a polar group such as a silanol group of a glass substrate due to the polar component of the polyester structure to improve the adhesion to the substrate. Furthermore, this specific compound crosslinks with the organosilicon compound (f-1) having an unsaturated group of (meth) acryloyloxy group during ultraviolet irradiation during color filter production or during high heat treatment, and further increases the adhesion to the substrate. It is thought that it can be improved.
Further, the urethane bond 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 bond or charge interaction to further improve the adhesion. It is thought that it can be done.

The compounds represented by the general formulas (b1) to (b4) are subjected to an addition reaction of lactones to a part or all of the hydroxyl groups of the polyhydric alcohol represented by the following general formulas (b1') to (b4'). It can then be obtained by (meth) acrylicization.

In the above formula, R ⁸ and R ⁹ are synonymous with the general formulas (a3) and (a4).

Examples of lactones to be added to the polyhydric alcohol include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, δ-valerolactone, α, α-dimethyl-. Examples thereof 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 having the structure represented by any of the general formulas (b1) to (b4) may be used alone or in combination of a plurality of compounds. Further, it can also be used in combination with a photopolymerizable monomer other than a compound having a structure represented by any of the general formulas (b1) to (b4), such as pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate. However, when a photopolymerizable monomer other than the compound having the structure represented by any of the general formulas (b1) to (b4) is used in combination, the general formulas (b1) to (b1) to (b1) in the photopolymerizable monomer (b) are used in combination. 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 developing solution to the exposed portion 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. When it is at least the above lower limit, the photocuring due to ultraviolet irradiation is improved and the alkali developability tends to be improved.

<Photopolymerization initiator (c)>
The photopolymerization initiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating 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 containing titanosen compounds described in JP-A-59-152396 and JP-A-61-151197; hexaarylbi 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, etc. Radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester derivatives described in JP-A-2000-80068, JP-A-2006-36750 and the like can be mentioned. ..

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

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

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

Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-Triazine and the like can be mentioned.

Examples of α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-). Morphorinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 4-dimethylaminoethylbenzoate, 4-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 can be mentioned.

As the photopolymerization initiator, oxime derivatives (oxime-based and keto-oxime-based compounds) are particularly effective in terms of sensitivity, and when an alkali-soluble resin containing a phenolic hydroxyl group is used, it is disadvantageous in terms of sensitivity. In some cases, such highly sensitive oxime derivatives (oxime-based and keto-oxime-based compounds) are particularly useful. Among the oxime derivatives, the oxime ester is particularly preferable from the viewpoint of adhesion to the substrate.
The photopolymerization initiator of oxime ester has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in its structure, so that it is highly sensitive to a small amount and is resistant to thermal reactions. It is possible to design a photosensitive resin composition that is stable and highly 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 is more preferable. Currently, the market demands a thin BM (black matrix) with a high degree of shading, and the pigment concentration is also increasing. It is especially effective in such situations.

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

Examples of the oxime-based compound include a compound containing a structural portion represented by the following general formula (22), and preferably an oxime ester-based compound represented by the following general formula (23).

In the above formula (22), R ²² may be substituted with an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and a carbon number of carbon atoms. 3 to 8 cycloalkanoyl groups, 3 to 20 carbons alkoxycarbonyl alkanoyl groups, 8 to 20 carbon phenoxycarbonyl alkanoyl groups, 3 to 20 carbon heteroaryloxycarbonyl alkanoyl groups, 2 to 10 carbon carbons It represents 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 the formula (23), R ^21a is hydrogen, or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, and a heteroarylalkyl group having 1 to 20 carbon atoms, which may be substituted respectively. , An alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or a heteroarylthioalkyl group having 1 to 20 carbon atoms, and an aminoalkyl having 1 to 20 carbon atoms. 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, allylloyl group having 7 to 20 carbon atoms, heteroallyloyl group having 1 to 20 carbon atoms, An alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms is shown.
R ^21b represents any substituent, including aromatic or heteroaromatic rings.

R ^21a may ^{form a ring together with R 21b} , and the linking group thereof may be an alkylene group having 1 to 10 carbon atoms and a polyethylene group (-(CH = CH) _{r), each of which may have a substituent.} −), Polyethynylene group (− (C≡C) _r −) or a group formed by combining these groups can be mentioned (note that r is an integer of 0 to 3).
R ^22a represents the same group as ^{R 22} in the above formula (22).
^{The R 22} in the general formula (22) ^{and the R 22a} in the general formula (23) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, and 3 to 8 carbon atoms. Cycloalkanoyl group is mentioned.

^{The R 21a} in the above general formula (23) is preferably substituted with an unsubstituted linear alkyl group such as a methyl group, an ethyl group or a propyl group, a cycloalkylalkyl group, or an N-acetyl-N-acetoxyamino group. Propyl group can be mentioned.
^{Further, examples of R 21b} in the above general formula (23) include a carbazole group which may be substituted, a thioxanthonyl group which may be substituted, and a phenylsulfide group which may be substituted.

As the oxime ester photopolymerization initiator (c), one containing a carbazole group which may be substituted as ^{R 21b is more preferable for the above-mentioned reason.} Further, 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 a substituent. 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 may be preferable. In particular, a carbazole group having at least one group selected from the group consisting of a benzoyl group, a toluoil group, a naphthoyl group, a thienylcarbonyl group, and a nitro group is preferable. Further, it is desirable that these groups are bonded to the 3-position of the carbazole group.

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

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

Examples of the ketooxime compound include a compound containing a structural portion 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 is synonymous with ^{R 22} in the general formula (22).)

(In the above general formula (25), R ^23a may be substituted, respectively, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, and a heteroaryl having 1 to 20 carbon atoms. Alkyl group, alkoxycarbonylalkyl group with 3 to 20 carbon atoms, phenoxycarbonylalkyl group with 8 to 20 carbon atoms, alkylthioalkyl group with 2 to 20 carbon atoms, heteroaryloxycarbonylalkyl group with 1 to 20 carbon atoms or heteroally Lucioalkyl group, aminoalkyl group with 1 to 20 carbon atoms, alkanoyl group with 2 to 12 carbon atoms, alkenoyl group with 3 to 25 carbon atoms, cycloalkanoyl group with 3 to 8 carbon atoms, allylloyl group with 7 to 20 carbon atoms , A heteroarylloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms.

R ^23b represents any substituent, including aromatic or heteroaromatic rings.
In addition, R ^23a may ^{form a ring together with R 23b} , and the linking group thereof may be an alkylene group having 1 to 10 carbon atoms and a polyethylene group (-(CH = CH) _{r), each of which may have a substituent.} −), Polyethynylene group (− (C≡C) _r −) or a group formed by combining these groups can be mentioned (note that r is an integer of 0 to 3).

R ^24a may be substituted with an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, and carbon. Heteroallyloyl group having 3 to 20, 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. )
^{The R 24} in the general formula (24) ^{and the R 24a} in the general formula (25) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, and 3 to 8 carbon atoms. Cycloalkanoyl group and aryloyl group having 7 to 20 carbon atoms can be mentioned.

^{The R 23a} in the above general formula (25) preferably includes an unsubstituted ethyl group, a propyl group and a butyl group, and an ethyl group or a propyl group substituted with a methoxycarbonyl group.
^{Further, examples of R 23b} in the above general formula (25) include a carbazoyl group which may be substituted and a phenylsulfide group which may be substituted.
Specific examples of the ketooxime ester-based compound suitable for the present invention include, but are not limited to, the compounds exemplified below.

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

These oxime and ketooxime ester compounds are known compounds themselves, and are, for example, one of a series of compounds described in JP-A-2000-80068 and JP-A-2006-36750.
The above photopolymerization initiator may be used alone or in combination of two or more.

In addition, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butyl anthraquinone and 1-chloroanthraquinone. Classes; benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone; 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy Acetophenones such as -1- (p-dodecylphenyl) ketone, 2-methyl- (4'-methylthiophenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone Derivatives; thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diisopropylthioxanthone; p-dimethylamino An benzoate ester derivatives such as ethyl benzoate and ethyl p-diethylaminobenzoate; aclysine derivatives such as 9-phenylaclysine and 9- (p-methoxyphenyl) aclysine; phenazine derivatives such as 9,10-dimethylbenzphenazine. ; Anthrone derivatives such as benzanthrone can also be mentioned.
Among these photopolymerization initiators, oxime ester derivatives are particularly preferable for the reasons described above.

<Sensitizer>
If necessary, the photopolymerization initiator may be used in combination with a sensitizing dye according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. Examples of these sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, and coumarin dyes having a heterocycle described in JP-A-3-239703 and JP-A-5-289335. 3-Ketokumarin compounds described in Kaihei 3-239703 and 5-289335, pyrromethene dyes described in JP-A-6-19240, and others, JP-A-47-2528, No. 54-155292, Tokusho-sho. No. 45-373777, No. 48-84183, No. 52-112681, No. 58-15503, No. 60-88005, No. 59-560403, No. 2-69, JP-A-57-168888 No., JP-A-5-107761, JP-A-5-210240, JP-A-4-288818, and the like having a dialkylaminobenzene skeleton can be mentioned.

Among these sensitizing dyes, preferable ones are amino group-containing sensitizing dyes, and more preferable ones are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone. , 3,4-Diaminobenzophenone and other benzophenone compounds; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1, 3,4-Thiazazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, ( It is a p-dialkylaminophenyl group-containing compound such as p-diethylaminophenyl) pyrimidine.
The most preferred of these is 4,4'-dialkylaminobenzophenone.
The sensitizing dye may also be used alone or in combination of two or more.

The content of the photopolymerization initiator (c) is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.% by mass, based on the total solid content of the photosensitive resin composition of the present invention. It is 7% by mass or more, usually 30% by mass or less, preferably 20% by mass or less. If the content of the photopolymerization initiator (c) is too small, the sensitivity may decrease, and if it is too large, the solubility of the unexposed portion in the developing solution decreases, and development defects are 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, and more preferably 90% by mass or more. By setting the value to the lower limit or higher, when the organosilicon compound (f-1) of the present invention is combined with the alkali-soluble resin as the photosensitive resin composition of the present application, the adhesion to the substrate is further improved after irradiation with ultraviolet rays. There is a tendency to be able to do it.

When an accelerator is used together with the photopolymerization initiator (c), the content of the accelerator is usually 0% by mass or more, preferably 0.02% by mass, based on the total solid content of the photosensitive resin composition of the present invention. As described above, it is usually 10% by mass or less, preferably 5% by mass or less, and the ratio of the accelerator is 0.1 to 50% by mass, particularly 0.1 to 10% by mass with respect to the photopolymerization initiator (c). It is preferable to use in. If the blending ratio of the photopolymerization initiator-based component consisting of the photopolymerization initiator (c) and the accelerator or the like is extremely low, it may cause a decrease in sensitivity to exposed light, and conversely, if it is extremely high, the unexposed portion is developed. Solubility in liquid may decrease, leading to poor development.

When a sensitizing dye is used, the blending ratio of the sensitizing dye in the photosensitive resin composition of the present invention is usually 0 to 20% by mass, preferably 0 to 0, based on the total solid content in the photosensitive resin composition. It is 15% by mass, more preferably 0 to 10% by mass.

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

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

Specific examples of pigments that can be used in the present invention are shown below by pigment numbers. The terms such as "CI Pigment Red 2" listed below mean the color index (CI).
Examples of the red pigment 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, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Among these, preferably C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, 254 can be mentioned.

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

Examples of the yellow pigment 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, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 can be mentioned. Among these, preferably C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.

As the orange pigment, C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 can be mentioned. Among these, preferably, C.I. I. Pigment Orange 38, 71 can be mentioned.

As the purple pigment, C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned. Among these, preferably C.I. I. Pigment Violet 19, 23, more preferably C.I. I. Pigment Violet 23 can be mentioned.

When the photosensitive resin composition of the present invention is a photosensitive resin composition for a resin black matrix of a color filter, a black coloring material can be used as the coloring material (d). The black color material may be a black color material alone or a mixture of red, green, blue and the like. Further, these coloring materials can be appropriately selected from inorganic or organic pigments and dyes.
Color materials that can be mixed and used to prepare black color materials include Victoria Pure Blue (42595), Auramine O (41000), Cachiron Brilliant Flavin (Basic 13), Rhodamine 6 GCP (45160), and Rhodamine B (45170). , Safranin OK 70: 100 (50240), Eriograusin X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Simler First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Simler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fastgen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionol Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (Note that the numbers in parentheses above mean the color index (CI)).

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

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

Made by Mitsubishi Chemical Corporation: MA7, MA77, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350 , # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B Degussa: Printex (registered trademark. Same.) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, PrintexL, PrintexG , 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 manufactured by Cabot Corporation: Monarch (registered trademark 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademarks; same below) 99, REGAL99R, REGAL REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN® XC72R, ELFTEX®-8

Made by Colombian Carbon: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN1890H, RAVEN1000, RAVEN10URA RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
As an example of another black pigment, titanium black, aniline black, iron oxide-based black pigment, and organic pigments of three colors of red, green, and blue can be mixed and used as the black pigment.

As the carbon black, one coated with a resin may be used. The use of carbon black coated with resin has the effect of improving the adhesion to the glass substrate and the volume resistance value. As the carbon black coated with the resin, for example, the carbon black described in JP-A-09-71733 can be preferably used.
The carbon black to be coated preferably has a total content of Na and Ca of 100 ppm or less. Carbon black is usually raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulation water, Na mixed from the furnace material of the reaction furnace, Ca, K, Mg, Al, Fe, etc. Contains ash in the order of percent. Of these, Na and Ca are generally contained in an amount of several hundred ppm or more, but if they are present in large amounts, they permeate into the transparent electrode (ITO) and other electrodes, causing an electrical short circuit. This is because it may become.

As a method for reducing the content of ash containing Na and Ca, carefully selected raw material oil, fuel oil (or gas) and reaction termination water for producing carbon black, which have the lowest possible content. This is possible by reducing the amount of alkaline substances added to adjust the structure as much as possible. As another method, there is a method of washing the carbon black produced from the furnace with water, hydrochloric acid or the like to dissolve and remove Na and Ca.

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

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

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

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

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

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

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

The present invention is particularly effective in the region where the pigment concentration of the black pigment is high. Especially in recent years, it is necessary to increase the black pigment concentration in order to increase the degree of shading. The content of the black pigment in the above-mentioned region having a large effect is in the region of 40% by mass or more with respect to the solid content of the colored photosensitive resin composition. When it is 45% by mass or more, the effect is larger, and when it is 50% by mass or more, the effect can be further exerted.

When the black pigment is contained in the photosensitive resin composition within the above content range, a colored photosensitive resin composition having a high light-shielding property (optical density, OD value) can be obtained. Specifically, by setting the content of the black pigment to 45% by mass or more, the optical density when a black matrix having a thickness of 1 μm is formed using the photosensitive resin composition of the present invention is 4.0 or more. Can be a value. The optical density is more preferably 4.2 or more. In the region with high light-shielding property, ultraviolet rays are difficult to penetrate deeply, and cross-linking by photopolymerization is weak especially in the portion where the substrate and the fine wire are in close contact, but when the photosensitive resin composition of the present application is used, the pigment concentration is particularly high. In large cases, the effect of the present application can be confirmed well. As the pigment concentration, 40 to 65% by mass is particularly effective. If the content of the coloring material is too small, the film thickness with respect to the color density becomes too large, which may adversely affect the gap control at the time of forming a liquid crystal cell. On the contrary, if the content of the coloring material is too large, sufficient image forming property may not be obtained.

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

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

Examples of the polymer dispersant include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of monomers having amino groups and macromonomers, and polyoxyethylene alkyl ethers. Examples thereof include dispersants, polyoxyethylene diester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

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

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

As described above, the organosilicon compound (f-1) of the present invention has its organic silane moiety, urethane binding site, and ethylenically unsaturated group moiety acting synergistically at high temperature and high humidity or at room temperature. Improves the 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 polymer dispersant by an affinity such as a hydrogen bond, and further improve the adhesion to the substrate. Be done. Therefore, a urethane-based polymer dispersant is particularly preferable for 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, 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-based polymer dispersants include Disperbyk 160 to 167, 182 series (all urethane-based), Disperbyk 2000, 2001 (all acrylic-based) (all manufactured by Big Chemie). Disperbyk 167, 182 and the like are examples of urethane-based polymer dispersants having the above-mentioned basic functional groups and having polyester and / or polyether bonds, which are preferable for obtaining a weight average molecular weight of 30,000 or less.

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

Examples of the above polyisocyanate compounds include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, trizine diisocyanate and the like. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanate such as dimerate diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), ω, ω Alicyclic diisocyanate such as ′-diisosinate dimethylcyclohexane, aliphatic diisocyanate having aromatic ring such as xylylene diisocyanate, α, α, α ′, α ′-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1, 6,11-Undecantriisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate Such as triisocyanates, trimerics thereof, water adducts, and polyol adducts thereof. The polyisocyanate is preferably a trimer of organic diisocyanate, and most preferably a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate. One of these may be used alone, or two or more thereof may be used in combination.

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

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

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

The polyether ester diol is obtained by reacting an ether group-containing diol or a mixture with another glycol with a dicarboxylic acid or an anhydride thereof, or by reacting a polyester glycol with an alkylene oxide, for example, poly (poly). Oxytetramethylene) adipate and the like can be mentioned. The most preferable polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

As polyester glycol, dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, etc.) Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol , 2-Methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1 , 6-Hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2 , 5-Hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, aliphatic glycols such as 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, xyl A product obtained by polycondensing with aromatic glycols such as len glycol and bishydroxyethoxybenzene, N-alkyldialkanolamine such as N-methyldiethanolamine), for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate. , Polylactone / propylene adipate, etc., or polylactone diols or polylactone monools obtained by using the diols or monovalent alcohols having 1 to 25 carbon atoms as an initiator, such as polycaprolactone glycol, polymethylvalerolactone, and these. A mixture of two or more kinds can be mentioned. The most preferable polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator.

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

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

The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, a heterocyclic structure, and more specifically, an imidazole ring or a triazole ring.
To exemplify such a compound having an active hydrogen and a tertiary amino group in the same molecule, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-Butandiamine and the like.

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

Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. Specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole and 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1. , 2,4-Triazole, 4-amino-4H-1,2,4-Triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-Diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole preferable.

One of these may be used alone, or two or more thereof may be used in combination.
The preferable blending ratio of the raw material 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. ~ 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, 0.2 to 25 parts by mass, preferably 0.3 parts by mass of the compound having an active hydrogen and a tertiary amino group in the same molecule. ~ 24 parts by mass.

The urethane-based polymer dispersant is produced according to a known method for producing a polyurethane resin. The solvent for production is usually ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate and cellosolve acetate, benzene, toluene, xylene and hexane. Hydrocarbons such as, diacetone alcohol, isopropanol, second butanol, some alcohols such as tertiary butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl. An aprotic polar solvent such as pyrrolidone or dimethylsulfoxide is used. One of these may be used alone, or two or more thereof may be used in combination.

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

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

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

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

(Acrylic polymer dispersant)
The acrylic polymer dispersant includes an unsaturated group-containing monomer having a functional group (the functional group referred to 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 known methods.

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

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, and isobutyl ( Meta) 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-cyclohexylmaleimide, N-phenylmaleimide, N N-substituted maleimides such as −benzyl maleimide, acrylonitrile, vinyl acetate and polymethyl (meth) acrylate macromonomers, polystyrene macromonomers, poly2-hydroxyethyl (meth) acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, poly Examples thereof include macromonomers such as caprolactone macromonomers. One of these may be used alone, or two or more thereof may be used in combination.

(Acrylic block copolymer)
In the photosensitive resin composition of the present invention, an acrylic block copolymer containing a nitrogen atom may be used as the dispersant in order to improve the dispersibility of the colorant and the dispersion stability. In such an acrylic block copolymer containing a nitrogen atom, the nitrogen atom contained therein has an affinity for the surface of the colorant, and the portion other than the nitrogen atom enhances the affinity for the medium as a whole. It is presumed to contribute to the improvement of dispersion stability.
The performance of the dispersant is its adsorption behavior on the solid surface. The detailed mechanism of the reason why block copolymers are excellent in adsorption behavior is unknown, but the following can be inferred.

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

Acrylic block copolymers containing nitrogen atoms are preferable because the colorants used in the present invention can be dispersed extremely efficiently. The reason is not clear, but it is presumed that because the molecular arrangement is controlled, there are few structures that hinder the adsorption of the dispersant to the colorant. The acrylic block copolymer is an AB block copolymer composed of an A block having a quaternary ammonium base and / or an amino group in the side chain and a B block having no quaternary ammonium base and an amino group. And / or BAB block copolymers are preferred.

If 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 It represents an atom or an optionally substituted cyclic or chain hydrocarbon group, or ^{two or more of R 51} , R ⁵² and R ⁵³ may be bonded to each other to form a cyclic structure. .M ^- is represented by the representative) a counter anion.. This quaternary ammonium base may be directly bonded to the main chain, or may be bonded to the main chain via a divalent linking group.

In −N ⁺ R ⁵¹ R ⁵² R ⁵³ , ^{as a cyclic structure formed by bonding two or more of R 51} , R ⁵² and R ⁵³ to each other, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a nitrogen-containing heterocyclic monocycle or Examples thereof include a fused ring formed by condensing two of these. The nitrogen-containing heterocycle preferably has no aromaticity, and more preferably a saturated ring. Specifically, for example, the following can be mentioned. These cyclic structures may further have substituents.

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.
Further, as the A block having a quaternary ammonium base, one containing a partial structure represented by the following general formula (VI) is particularly preferable.

In the above formula (VI), R ⁵¹ , R ⁵² , and R ⁵³ each independently represent a hydrogen atom or a cyclic or chain hydrocarbon group which may be substituted. Alternatively, ^{two or more of R 51} , R ⁵² and R ⁵³ may be bonded to each other to form an annular structure. R ⁵⁴ represents a hydrogen atom or a methyl group. X represents a divalent linking group, M ^- represents a counter anion.
In the above general formula (VI), ^{the hydrocarbon groups of R 51} , R ⁵² , and R ⁵³ are independently substituted groups having an alkyl group having 1 to 10 carbon atoms and an aromatic group having 6 to 20 carbon atoms, respectively. preferable. Specific examples thereof 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, for example, an alkylene group, an arylene group having 1 to 10 carbon ^{atoms, -CONH-R 55 -, -} COO-R 56 - ( where, R ⁵⁵ and R ⁵⁶ is 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 independently alkylene groups). . represented) and the like, preferably -COO-R ⁵⁶ - is.

Further, the counter anion of M ^{- The, Cl -, Br -, I} -, ClO 4 -, BF 4 -, CH 3 COO -, PF 6 - , and the like.
Two or more kinds of partial structures containing a specific quaternary ammonium base as described above may be contained in one A block. In that case, the two or more kinds of quaternary ammonium base-containing partial structures may be contained in the A block in any mode of random copolymerization or block copolymerization. Further, the partial structure containing no 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-based monomer described later. Be done.

The content of the quaternary ammonium base-free partial structure in the A block is preferably 0 to 50% by mass, more preferably 0 to 20% by mass, but the quaternary ammonium base-free partial structure is Most preferably, it is not contained in the A block.
The A block of the acrylic block copolymer described above may have an unreacted tertiary amino group that has not been quaternized.

When the A block has an amino group, the amino group may be any of the 1st to 3rd grades. The content ratio of the monomer having a 1st to 3rd grade amino group is preferably 20 mol% or more, more preferably 50 mol% or more in the monomer composition constituting the acrylic block copolymer. % Or more.
This amino group may be directly bonded to the main chain, or may be bonded to the main chain via a divalent linking group.

The primary to primary amino groups are preferably −NR ⁶¹ R ⁶² (where R ⁶¹ and R ⁶² are cyclic or chain alkyl groups which may independently have substituents, respectively. An aryl group which may have a substituent or an aralkyl group which may have a substituent is shown), and a preferable partial structure (repetition unit) containing the aryl group is, for example, the following. Examples thereof include structures represented by general formulas.

However, R ⁶¹ and R ⁶² are synonymous with the above R ⁶¹ and R ^{62 , R 63} indicates an alkylene group having 1 or more carbon atoms, and R ⁶⁴ indicates 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 and 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.
Further, the partial structure containing the amino group may be contained in two or more kinds in one A block. In that case, the two or more kinds of amino group-containing partial structures may be contained in the A block in any mode of random copolymerization or block copolymerization. Further, a partial structure containing no 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-based monomer. .. The content of the amino group-free partial structure in the A block is preferably 0 to 50% by mass, more preferably 0 to 20% by mass, but the amino group-free partial structure is contained in the A block. Most preferably it is not included.

The A block may have either a quaternary ammonium base or an amino group, or both.
On the other hand, if the B block constituting the acrylic block copolymer does not have the above-mentioned quaternary ammonium base and amino group and is composed of a monomer copolymerizable with the above-mentioned monomer constituting the A block, There are no particular restrictions. The B block is a pro-solvent site that does not have a nitrogen atom-containing functional group that serves as a pigment adsorbing group, and since it has an affinity for a solvent, it has a function of stabilizing the pigment adsorbed on the dispersant in the solvent. ..

Examples of the B block include styrene-based monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (meth) propyl acrylate, isopropyl (meth) acrylate, and (meth) acrylic. Butyl acid, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethylacrylate, N, N-dimethylaminoethyl (Meta) acrylic acid ester-based monomers such as (meth) acrylate; (meth) acrylate-based monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N , N-Dimethylaminoethyl acrylamide and other (meth) acrylamide-based monomers; vinyl acetate; acrylic nitrile; allyl glycidyl ether, glycidyl crotonate ether; N-methacryloyl morpholine, and other comonomer copolymerized polymer structures.

As the B block, one containing a partial structure derived from a (meth) acrylic acid ester-based 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 structures derived from the (meth) acrylic acid ester-based monomer may be contained in one B block. Of course, the B block may further contain a partial structure other than these. When partial structures derived from two or more kinds of monomers are present in a B block containing no quaternary ammonium base, each partial structure is contained in the B block in either a random copolymerization or a block copolymerization manner. You may.

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

Living polymerization methods include anionic living polymerization methods, cationic living polymerization methods, and radical living polymerization methods. For example, the method described in Japanese Patent Application Laid-Open No. 2007-270147 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 preferable range is when the A block has a quaternary ammonium base and when it does not. Is different. The amine value is a value expressed in mg of KOH corresponding to the molar equivalent of the acid required to neutralize the amino group in 1 g of the copolymer.

That is, in the AB block copolymer and the BAB 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 0.1 to 10 mmol, and outside this range, good heat resistance and dispersibility may not be available.
In addition, such a block copolymer may usually contain an amino group generated 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 to 50 mgKOH / g.

When the A block does not contain a quaternary ammonium base, 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 or absence and type of an acidic group that is the source of the acid value, but is generally preferably low, usually 100 mgKOH / g or less, and preferably 50 mgKOH / g. It is 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-equivalent weight average molecular weight (Mw) measured by GPC. If the molecular weight of the acrylic block copolymer is too small, the dispersion stability tends to decrease, and if it is too large, the developability and resolution tend to decrease.
In the present invention, a commercially available acrylic block copolymer having a structure similar to that described above can also be applied.

(Graft copolymer containing nitrogen atom)
As the graft copolymer containing a nitrogen atom, one having a repeating unit containing a nitrogen atom in the main chain is preferable. Above all, it is preferable to have a repeating unit represented by the following general formula (i) and / 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 and propylene, and is preferably an alkylene group having 2 to 3 carbon atoms. It is a group, more preferably an ethylene group. A represents a hydrogen atom or any of the following general formulas (iii) to (v), and is 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 the 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. It 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 the general formula (iv), G ¹ represents a divalent linking group, among which 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 Is 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 and hexyl, among which 2 to 5 carbon atoms such as ethyl, propyl, butyl and pentyl. (Preferably an alkyl group). 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 the general formula (v), W ³ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 hydroxyl groups and having 1 to 50 carbon atoms, and among them, an alkyl group having 10 to 20 carbon atoms such as stearyl. , A hydroxyalkyl group having 1 to 2 hydroxyl groups such as monohydroxystearyl and having 10 to 20 carbon atoms is preferable.)

The content of the repeating unit represented by the general formula (i) or (ii) in the graft copolymer containing a nitrogen atom is preferably high, and is usually 50 mol% or more in total, preferably 70 mol%. That is all. Both the repeating unit represented by the general formula (i) and the repeating unit represented by the general formula (ii) may be used in combination, and the content ratio thereof is not particularly limited, but is preferably the general formula (i). It is preferable that the repeating unit of i) is contained in a larger amount. The total number of repeating units represented by the general formula (i) or the 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. Below, 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 ends of -NH ₂ and -R ^91- NH ₂ (R ⁹¹ is synonymous with the general formulas (i) and (ii)).

In addition, as long as it is a graft copolymer as described above, the main chain may be linear or branched.

The mass average molecular weight of this 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 agglomeration of the coloring material cannot be prevented, and the color material may become highly viscous or gelled. If it exceeds 100,000, the color material itself becomes highly viscous, and It is not preferable because it lacks solubility in organic solvents.

As the method for synthesizing the dispersant, a known method can be adopted, and for example, the method described in Japanese Patent Publication No. 63-30057 can be used.

The content of the dispersant is usually 50% by mass or less, preferably 30% by mass or less, usually 1% by mass or more, and preferably 3% by mass or more in the solid content of the photosensitive resin composition. The content of the dispersant is usually 5% by mass or more, particularly preferably 10% by mass or more, and usually 200% by mass or less, particularly preferably 80% by mass or less, based on the coloring material (d). If the content of the dispersant is too small, sufficient dispersibility may not be obtained, and if it is too large, the proportion of other components tends to decrease relatively, and the color density, sensitivity, film forming property, etc. tend to decrease. is there.

In particular, as the dispersant, it is preferable to use a polymer dispersant and a pigment derivative in combination. 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. It is preferably 1% by mass or more, usually 10% by mass or less, preferably 5% by mass or less.
When a surfactant is used, its content is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, still more preferably 0.01, based on the total solid content in the photosensitive resin composition. ~ 0.5% by mass, most preferably 0.03 to 0.3% by mass. If the content of the surfactant is less than the above range, the smoothness and uniformity of the coating film may not be exhibited, and if it is too large, the smoothness and uniformity of the coating film cannot be exhibited and other properties deteriorate. In some cases.
The photosensitive resin composition of the present invention is prepared by using the above-mentioned organic solvent so that the solid content concentration is usually 5 to 50% by mass, preferably 10 to 30% by mass.

<Thiols>
In the photosensitive resin composition of the present invention, it is preferable to add thiols in order to increase the sensitivity and the adhesion to the substrate. Types of thiols include hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and trimetyl propanthithioglycolate. , Butanediol Bisthiopropionate, Trimethylol Propanetristhiopropionate, Trimethylol Propanetristhioglycolate, Pentaerythritol Tetrakissthiopropionate, Pentaerythritol Tetrakissthioglycolate, Trishydroxyethyltristhiopropionate, Ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate); (PGMB for short), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryl) Oxy) butane; (trade name; Karenz MT BD1, manufactured by Showa Denko Co., Ltd.), butanediol trimethyl propanthryl (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate); (trade name; Karenz) MT PE1, manufactured by Showa Denko Co., Ltd., pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropanthris (3-Mercaptoisobutyrate), Trimethylol Propantris (3-Mercaptobutyrate); (TPMB for short) Trimethylol Propantris (2-Mercaptoisobutyrate); (TPMIB for short), 1, 3, 5 -Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion; (trade name: Karenz MT NR1, manufactured by Showa Denko Co., Ltd.), etc. These can be used alone or in admixture of two or more. Of these, polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1 are preferable, and among them, Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1 are more preferable, and Karenz MT PE1 is preferable. Especially preferable.

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. It is .5% by mass or more, usually 10% by mass or less, preferably 5% by mass or less. If the content of the thiol compound is too small, the sensitivity may decrease, and if it is too large, the storage stability may deteriorate.

<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 coloring material (d), and a dispersion. The agent (e) and various materials used as needed are used in a state of being dissolved or dispersed in an organic solvent.
As the organic solvent, it is preferable to select a solvent having a boiling point (under pressure 1013.25 [hPa] conditions; hereinafter, the boiling points are all the same) in the range of 100 to 300 ° C. More preferably, it is a solvent having a boiling point of 120 to 280 ° C.
Examples of such an organic solvent include the following.

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

Glycoldialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl Glycolalkyl ether acetates such as ether acetate, 3-methyl-3-methoxybutyl acetate;

Glycoldiacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamil ether, ethyl isobutyl ether, dihexyl ether;
Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methylnonyl ketone, methoxymethylpentanone. Ketones;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amilformate, ethylformate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methylisobutyrate, ethylene glycol acetate, ethyl propionate, propylpropionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Chain or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid;

Halogenated hydrocarbons such as butyl chloride, amilk chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:
Commercially available solvents corresponding to the above include Mineral Spirit, Barsol # 2, Apco # 18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2. Solvento # 150, Shell TS28 Solvent, Calbitol, Ethylcarbitol, Butylcarbitol, Methylcellosolve (“Cellosolve” is a registered trademark; the same shall apply hereinafter), Ethylcellosolve, Ethylcellosolve acetate, Methylcellosolve acetate, Diglime (any of them) (Product name) and so on.

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

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

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

The content ratio 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, the coloring material may precipitate and solidify at the tip of the slit nozzle to cause foreign matter defects, and if it is too large, the drying temperature of the composition becomes slow, and the color described later In the filter manufacturing process, there is a concern that it may cause problems such as poor tact in the vacuum drying process and pin marks of pre-bake.

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, the high boiling point solvent having a boiling point of 150 ° C. or higher is not separately contained. It doesn't matter.
As a preferable high boiling solvent, for example, among the various solvents described above, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanoldi 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 from the viewpoint of ease of application and viscosity stability, it is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably. It is 10% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less.

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

(Adhesion improver)
In order to improve the adhesion to the substrate, an adhesion improver other than the organosilicon compound (f) may be contained in the photosensitive resin composition of the present invention, for example, a phosphoric acid-based adhesion improver and other adhesion improvers. Agents and the like can be mentioned.

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

In the above general formulas (g1), (g2) and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l'are integers of 1 to 10, and m is 1, 2 or 3.
Examples of other adhesion improvers include TEGO ^* Add Bond LTH (manufactured by Evonik Industries). 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 kinds such as anionic type, cationic type, nonionic type, amphoteric surfactant and the like can be used. Among them, it is preferable to use a nonionic surfactant because it is unlikely to adversely affect various properties, and among them, a fluorine-based or silicon-based surfactant is effective in terms of coatability.

Examples of such surfactants include TSF4460 (manufactured by GE Toshiba Silicone), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by Big Chemie), and KP340 (Shinetsu Silicone). , F-470, F-475, F-478, F-559 (manufactured by Dainippon Ink and Chemicals), SH7PA (manufactured by Torre Silicone), DS-401 (manufactured by Daikin), L-77 (manufactured by Daikin) Examples include (manufactured by Nippon Unicar) and FC4430 (manufactured by Sumitomo 3M).
As the surfactant, one type may be used, or two or more types may be used in combination in any combination and ratio.

[Other ingredients]
In addition to the above components, the light-shielding photosensitive resin composition of the present invention further includes a polymerization accelerator, a photoacid generator, a cross-linking agent, a plasticizer, a storage stabilizer, a surface protectant, an organic carboxylic acid, and an organic carboxylic acid. It may contain an acid anhydride, a development improver, a thermal polymerization inhibitor and the like.
(Pigment derivative)
The photosensitive coloring composition of the present invention may contain a pigment derivative in order to improve dispersibility and storage stability. Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrone, perylene, perinone, diketopyrrolopyrrole, and dioxazine. Derivatives such as phthalocyanine are mentioned, and phthalocyanine and quinophthalone are particularly preferable.

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

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

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

When the coloring material (d) is dispersed by a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. The dispersion treatment conditions are such that the temperature is usually 0 ° C. to 100 ° C., preferably in the range of room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid, the size of the dispersion treatment apparatus, and the like. The guideline for dispersion is to control the gloss of the ink so that the 20-degree mirror gloss (JIS Z8741) of the resist is in the range of 100 to 200. When the glossiness of the resist is low, the dispersion treatment is not sufficient and coarse pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, etc. .. Further, if 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 above dispersion treatment and the above other components contained in the resist are mixed to obtain a uniform solution. In the resist manufacturing process, fine dust is often mixed in the liquid, so it is desirable to filter the obtained resist with a filter or the like.

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

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

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

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 physical properties such as adhesiveness. ..
The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. When thin film formation treatment of various resins is performed, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

(2) Black Matrix In order to form the black matrix of the present invention with the above-mentioned photosensitive resin composition of the present invention, the photosensitive resin composition of the present invention is applied onto a transparent substrate, dried, and then the sample is formed. A photomask is placed on the photomask, and a black matrix is formed by image exposure, development, and if necessary, thermosetting or photocuring through the photomask.

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

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

(3-2) Drying of coating film 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. The drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably at a temperature of 50 to 130 ° C., depending on the type of solvent component, the performance of the dryer used, and the like. It is selected in the range of 30 seconds to 3 minutes.

The higher the drying temperature, the better the adhesiveness of the coating film to the transparent substrate. However, if the drying temperature is too high, the alkali-soluble resin may be decomposed to induce thermal polymerization, resulting in poor development. The drying step of this coating film may be a vacuum drying method in which the coating film is dried in a reduced pressure chamber without raising the temperature.
(3-3) Exposure Image exposure is performed by superimposing a negative mask pattern on a coating film of a photosensitive resin composition and irradiating a light source of ultraviolet rays or visible light through the mask pattern. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film. The light source used for the above image exposure is not particularly limited. Examples of the light source include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, argon ion lasers, and YAG lasers. Examples thereof include laser light sources such as an excimer laser, a nitrogen laser, a helium cadmium laser, and a semiconductor laser. An optical filter can also be used when irradiating light of a specific wavelength for use.

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

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

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

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

(3-5) Thermosetting Treatment The developed substrate is subjected to a thermosetting treatment or a photocuring treatment, preferably a thermosetting treatment. The thermosetting treatment conditions at this time are selected in the temperature range of 100 to 280 ° C., preferably in the range of 150 to 250 ° C., and the time is selected in the range of 5 to 60 minutes.
The width of the bottom of the black matrix formed as described above is usually 3 to 50 μm, preferably 4 to 30 μm, particularly preferably 4 to 8 μm in the case of high-thin wires, and the height is usually 0.5 to 5 μm, preferably 0.5 to 5 μm. Is 1 to 4 μm. The volume low efficiency is 1 × 10 ¹³ Ω · cm or more, preferably 1 × 10 ¹⁴ Ω · cm or more, and the relative permittivity is 6 or less, preferably 5 or less. Further, the optical density (OD) per 1 μm of 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]
A photosensitive coloring resin composition containing one of red, green, and blue coloring materials is applied onto a transparent substrate provided with a black matrix by the same process as in (3-1) to (3-5) above. After drying, a photomask is superposed on the coating film, and a pixel image is formed through the photomask by image exposure, development, and if necessary, heat curing or photocuring to create a colored layer. A color filter image can be formed by performing this operation on each of the three color photosensitive coloring resin compositions of red, green, and blue. These orders are not limited to the above.

[Colored spacer]
The colored photosensitive composition of the present embodiment can also be used as a resist for a colored spacer in addition to 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 Application Laid-Open No. 8-234212 It is described that the spacer has a light-shielding property. The colored spacer can be formed by the same method as the above-mentioned black matrix except that a mask for the colored spacer is used.

(3-6) Formation of transparent electrode A color filter is used as a part of parts such as a color display and a liquid crystal display device by forming a transparent electrode such as ITO on an image as it is, but the surface is smooth. If necessary, a top coat layer such as polyamide or polyimide can be provided on the image in order to improve the properties and durability. Further, in some applications such as a plane orientation type drive system (IPS mode), a 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 for displaying an image or a moving image, and examples thereof include a liquid crystal display device and an organic EL display described later.
[Liquid crystal display device]
The liquid crystal display device of the present invention is manufactured by using the above-mentioned black matrix of the present invention, and is not particularly limited in terms of the formation order and formation position of the color pixels and the black matrix.

In a liquid crystal display device, usually, an alignment film is formed on a color filter, a spacer is sprayed on the alignment film, a liquid crystal cell is formed by bonding with an opposing substrate, and a liquid crystal is injected into the formed liquid crystal cell. It is completed by connecting to the counter electrode. As the alignment film, a resin film such as polyimide is suitable. A gravure printing method and / or a flexographic printing method is usually adopted for forming the alignment film, and the thickness of the alignment film is several tens of nm. After the alignment film is hardened by heat firing, it is surface-treated by irradiation with ultraviolet rays or treatment with a rubbing cloth to obtain a surface state in which the inclination of the liquid crystal can be adjusted.

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

The gap for bonding to the facing substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After bonding to the facing substrate, the parts other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then depressurized in a vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. .. The degree of decompression in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ^-7 Pa, but preferably 1 × 10 ^-3 to 1 × 10 ^-6 Pa. Further, it is preferable to heat the liquid crystal cell at the time of depressurization, and the heating temperature is usually 30 to 100 ° C, more preferably 50 to 90 ° C. The warming retention at the time of depressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. In the liquid crystal cell into which the liquid crystal is injected, the liquid crystal display device (panel) is 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 type, an aliphatic type, or a polycyclic compound, and may be any of a liotropic liquid crystal, a thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, a nematic liquid crystal, a smestic liquid crystal, a cholesteric liquid crystal and the like are known, but any of them may be used.
[Organic EL display]
The organic EL display of the present invention is manufactured by using the color filter of the present invention.

When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 1, a pattern formed by a colored resin composition (that is, pixels 20 and adjacent pixels 20) is first placed on a transparent support substrate 10. A color filter in which a resin black matrix (not shown) provided between the pixels 20 is formed is produced, and the organic illuminant 500 is placed 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. At least one of the pixel 20 and the resin black matrix was produced by using the photosensitive colored resin composition of the present invention. As a method of laminating the organic luminescent material 500, a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter, or , A method of laminating the organic light emitter 500 formed on another substrate on the inorganic oxide film 40 and the like can be mentioned. Using the organic EL element 100 produced in this manner, for example, the method described in "Organic EL Display" (Ohmsha, August 20, 2004, Luminous, Shizushi Tokito, Chihaya Adachi, Hideyuki Murata), etc. Can produce an organic EL display.

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

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

<Adjustment of carbon black ink>
A pigment, a dispersant, a dispersion aid, and a solvent were mixed with the following composition, and the 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 amount ratios.
-Pigment: R1060 (Carbon black manufactured by Colombia); 100 parts by mass-Dispersant: BYK167 (Basic urethane dispersant manufactured by Big Chemie); 20 parts by mass (solid content conversion)
-Dispersion 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, these were sufficiently stirred and mixed to obtain a dispersion liquid.
Next, a paint shaker was used to perform dispersion treatment in the range of 25 to 45 ° C. for 6 hours. As the beads, zirconia beads having a diameter of 0.5 mm were used, and the beads were added at a ratio of 180 parts by mass to 60 parts by mass of the dispersion liquid. After the dispersion was completed, the beads and the dispersion liquid 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 an epoxy compound (epoxy equivalent 264) having the above structure, 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 with a thermometer, a stirrer, and a cooling tube. The mixture was placed in a flask and reacted at 90 ° C. with stirring until the acid value became 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
25 parts by mass of the epoxy acrylate solution, 0.76 parts by mass of trimethylolpropane (TMP), 3.3 parts by mass of biphenyltetracarboxylic acid anhydride (BPDA), 3.5 parts by mass of tetrahydrophthalic anhydride (THPA). Was placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.
When the resin solution became transparent, it was diluted with methoxybutyl acetate to prepare a solid content of 50% by mass, and the acid value was 115 mgKOH / g, and the polystyrene-equivalent weight average molecular weight (Mw) of 2600 measured by GPC was alkaline soluble. 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) were dissolved in 30 ml of dichloromethane, cooled to 2 ° C. in an ice-water bath and stirred, and AlCl ₃ (3. 41 g, 25.61 mmol) was added. After further 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, AlCl 3} (4.1 g, 30.73 mmol) was added, and the mixture was further added for 1 hour 30. 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 recovered organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a white solid (10 g) diketone compound.

(Oxime body)
The diketone compound (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 solution was concentrated, 30 ml of ethyl acetate was added to the obtained residue, the mixture was 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 a pale yellow solid oxime.

(Oxime ester)
Oxime (2.22 g, 4.77 mmol) and acetyl chloride (1.34 g, 17.0 mmol) were added to 20 ml of dichloromethane, ice-cooled, triethylamine (1.77 g, 17.5 mmol) was added dropwise, and 1 as it was. Time reacted. After confirming the disappearance of the raw material by thin layer chromatography, water was added to stop the reaction. The reaction mixture 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 is concentrated under reduced pressure, and the obtained residue is purified by column chromatography (ethyl acetate / hexane = 2/1) to obtain 0.79 g of a pale yellow solid photopolymerization initiator (1). Obtained. ^{The 1} H-NMR chemical shift of the photopolymerization initiator (1) is shown below.

^{1 1} H-NMR (CDCl ₃ ): σ1.17 (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.

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

(Organosilicon 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 with a tetramer weight ratio of 17: 1: 1: 1.

(Organosilicon 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 with a tetramer weight ratio of 1: 8: 8: 3.

These organosilicon compounds can be obtained by the method described in <Specific Organosilicon Compound (f)>.
These structures are ^{identified by 1} H-NMR, ¹³ C-NMR, IR, silica concentration by IPC light emitting device, elemental analysis of SEM-EDX, etc., and the ratio of monomer, 2, 3, and tetramer. Was identified from the area of the peaks separated by the liquid chromatogram and the parent ion peak of the mass spectrum gram of each peak.

( ^{1 1} H-NMR)
δ (ppm)
0.55 ppm (t, Si-CH ₂ , 2H)
1.55 ppm (m, -C-CH _2- C, 2H)
3.10ppm (q, CH _2- N, 2H)
3.50ppm (s, Si-OCH ₃ , about 9H)
_{4.25ppm (s, O-CH 2} -CH 2 -O, about 4H)
5.10ppm (s, NH, 1H)
5.7 to 6.5 ppm (m, C (= O) CH = CH ₂ , 3H)

(IR spectrum)
Characteristic absorption (cm ^-1 )
3350 (NH): 1726 (C = O): 1636, 1620 (C = C)

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

In addition, 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 the simple elemental analysis.

<Photopolymerizable monomer>
The following photopolymerizable monomers (b-I) to (b-V) were prepared.
b-I: 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 Industry Co., Ltd.)
b-VI Acrylic acid ester compound 6 of tris- (2-caprolactone ethyl) isocyanurate represented by the following structure (b16) (A-9300-1CL (manufactured by Shin Nakamura Chemical Industry Co., Ltd.))
b-VII Acrylic acid ester compound 7 of tris- (2-caprolactone ethyl) isocyanurate represented by the following structure (b17) (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

<Example 1>
(Preparation of black resist 1)
Using the carbon black ink adjusted in <Adjustment of carbon black ink>, each component shown in Table 1 was added at the ratio shown in Table 1, and the mixture was stirred and dissolved by a stirrer to prepare a 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 a biphenyl epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC3000H) and reacting with tetrahydrophthalic hydride. It has an ethylenically unsaturated group and a carboxylic acid group. Acid value 99 mgKOH / g, polystyrene-equivalent weight average molecular weight (Mw) 6400 measured by GPC. Dipentaerythritol hexaacrylate: KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.

<Examples 2 to 3>
(Preparation of black resist 2-3)
Black resists 2 and 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 shown in Table 2-1.

<Examples 4 to 7 and 9 to 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 monomer shown in Tables 2-1 and 2. ..

<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 the organosilicon compound was not added in Example 1.

<Comparative Examples 2 to 4>
(Preparation of comparative black resists 2-4)
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 used as a commercially available silane coupling agent shown 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-Isocyanatepropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Evaluation of resist)
(1) Preparation 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 on a hot plate at 100 ° C. for 120 seconds. .. Subsequently, the obtained dry coating film was subjected to pattern exposure through an exposure mask at 40 mJ with a high-pressure mercury lamp, and then subjected to alkaline 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 developing with a solution for 1.6 times the dissolution time. Then, post-baking was performed in an oven at 230 ° C. for 30 minutes to prepare a black matrix having a film thickness of about 1 μm. The dissolution time was the time during which the photosensitive layer in the unexposed portion was dissolved and the entire substrate was visible during the current treatment, and the dissolution time of each black resist and the comparative black resist was 30 to 60 seconds.

(2) Light-shielding degree: Evaluation of optical density (OD value) and film thickness of BM A step measuring device for measuring the film thickness of BM produced in (1) using the prepared black resists 1 to 11 and comparative black resists 1 to 4. The measurement was performed with an Alpha-Step-500 (KLA-Tencor), and the OD value was measured with a transmission concentration measuring device GretagMacbeth D200-II (GretagMacbeth). When the OD value (unit OD value) per 1 μm was obtained from this, the BMs produced by the black resists 1 to 11 were all 4.2 / μm.

(3) Substrate adhesion evaluation (under high temperature and high humidity)
The substrate adhesion under high temperature and high humidity was evaluated with a black matrix prepared as follows using the prepared black resists 1 to 11 and comparative black resists 1 to 4.
Specifically, in "(1) Preparation of black matrix (BM)", a 5 cm square of a black matrix having a film thickness of 1.20 μm was used in the same process except that a mask was not used at the time of exposure and no development treatment was performed. A solid plate was formed. It was exposed for 2 hours in a water vapor atmosphere at 120 ° C., 2 atmospheres and 100% relative humidity (pressure cooker test, PCT). After that, the surface was cross-cut in 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 by JIS-K5600-5-6. The state of peeling at that time was evaluated according to the following criteria.

(Substrate adhesion evaluation criteria)
⊚: No peeling at the substrate / BM interface due to tape peeling after PCT. No peeling of the BM surface.
◯: After PCT, peeling of the BM surface was observed minutely due to tape peeling, but there was no peeling at the substrate / BM interface.
Δ: After PCT, peeling at the substrate / BM interface is observed due to tape peeling. It exceeds 0% and is within 10% of the evaluation area.
X: After PCT, peeling at the substrate / BM interface is observed due to tape peeling. It exceeds 10% and is within 40% of the evaluation area.
XX: After PCT, peeling at the substrate / BM interface is observed due to tape peeling. More than 40% and less than 100% of the evaluated area.
XXX: After PCT, peeling at the substrate / BM interface is observed on the entire substrate due to tape peeling.

(4) Substrate adhesion evaluation (room temperature)
The substrate adhesion at room temperature was evaluated with a black matrix prepared 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 a black matrix with a film thickness of 1.20 μm was used in the same process except that a mask was not used during exposure and no development treatment was performed in "(1) Preparation of black matrix (BM)". Was formed, and an aluminum stud pin (manufactured by Quad) was joined using a sealing agent (manufactured by Mitsui Chemicals, Inc.) to prepare a sample for measurement. A tensile test was performed on the sample using Romulus (manufactured by Quad) at a speed of 2.0 kg / s, and the adhesion stress was determined by the following formula from the fracture strength and adhesive area when the black matrix and the glass substrate were fractured. I asked.
Adhesion stress (kg / cm ² ) = breaking strength (kg) / adhesive area (cm ² )
The results are shown in Tables 2-1 and 2-2. The substrate adhesion force (%) in Tables 2-1 and 2-2 was obtained as a relative value (%) when the substrate adhesion force in Comparative Example 1 was 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 and the substrate are formed 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) which are a mixture of the silane monomer of the general formula (2) and the silane oligomer of the general formula (3). As mentioned 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 the BM under high temperature and high humidity becomes very good, and It is considered that the adhesion between the substrate and the BM was good even at room temperature.

Further, Examples 4 to 7, 9 to 11 in which not only the organosilicon compound (f-1) but also the polyfunctional (meth) acrylate monomer having a caprolactone structure as the photopolymerizable monomer (b) is used are the 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 between them, further improving the substrate adhesion effect under high temperature and high humidity, and at room temperature. 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 contain an epoxy group of other organosilicon compounds. Since it contains only (meth) acryloyloxy groups and isocyanate groups, it is not possible to obtain a synergistic effect due to the urethane bond site, and it has a large substrate adhesion under high temperature and high humidity or room temperature as seen in the examples. No improvement was seen.

Claims (14)

Alkali-soluble resin (a), photopolymerizable monomer (b), photopolymerization initiator (c), coloring material (d)
), The dispersant (e) and the organosilicon compound (f).
The organosilicon compound (f) contains at least the organosilicon compound (f-1) having a structure represented by the following general formula (1).
A photosensitive resin composition, wherein the photopolymerizable monomer (b) contains a compound represented by at least one of the following general formulas (b1) to (b4).

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

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

(In the above formula, R ^b is a group represented by the following formula (b5), R ⁸ is an alkyl group having 1 to 6 carbon atoms, R ⁹ is an alkylene group having 1 to 10 carbon atoms, and 7 to 10 carbon atoms. Allylene alkylene group,
Alternatively, it is an arylene group having 6 to 10 carbon atoms. )

(In the formula, R ⁶ is a carbon number of is 2-6, represent an alkylene group having no branch, .m R ⁷ is representing a hydrogen atom or a methyl group is .m represents an integer of 0 to 3 2 Or, in the case of 3, a plurality of R ^6s may be the same or different.
However, m is 1 in at least one ^{of the plurality of R b} contained in the above formula (b1).
Of R b which is an integer of ~ 3 and is included in a plurality of R ^{b in} the above formula (b2), m is an integer of 1 to 3 in at least one of them, and among a plurality of R ^{b contained in the above formula (b3).} , At least 1
In each case, m is an integer of 1 to 3, and m is an integer of 1 to 3 in at least one of ^{R b contained in the above equation (b4).} ) The photosensitive resin composition according to claim 1, wherein the organosilicon compound (f-1) contains an organosilicon compound represented by the following general formula (2).

(In the above formula, R ¹ and ^Ra are synonymous with the general formula (1). A plurality of R ¹ included in the formula may be the same or different from each other.) The photosensitive resin composition according to claim 1 or 2, wherein the organosilicon compound (f-1) contains an organosilicon compound represented by the following general formula (3).

(In the above formula, R ¹ and ^Ra are synonymous with the general formula (1). In addition, n represents an integer of 2 to 10. R ¹ and R ^a included in a plurality of formulas are the same. It may be different.) The photosensitive resin composition according to any one of claims 1 to 3, wherein the photopolymerization initiator (c) is an oxime ester. The photosensitive resin composition according to any one of claims 1 to 4, wherein the coloring material (d) is a black coloring material. The photosensitive resin composition according to any one of claims 1 to 5, wherein the content of the coloring material (d) is 40% by mass or more with respect to the total solid content. 1. The dispersant (e) is a polymer dispersant having a basic functional group.
The photosensitive resin composition according to any one of No. 6 to 6. The photosensitive resin composition according to any one of claims 1 to 7, wherein the alkali-soluble resin (a) contains an ethylenically unsaturated group. The photosensitive resin composition according to claim 8, 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 is the following epoxy (meth) acrylate resin (A1-1) and / or the following epoxy (meth) acrylate resin (
The photosensitive resin composition according to claim 9, which contains A1-2).
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 polybasic acid and polybasic acid and / Or an epoxy (meth) acrylate resin obtained by reacting its anhydride. Epoxy (meth) acrylate resin (A1-2): An α, β-unsaturated monocarboxylic acid or α having a carboxyl group in the epoxy resin. , Β-Unsaturated monocarboxylic acid ester added, and further reacted with polyvalent alcohol with polybasic acid and / or its anhydride to obtain an epoxy (meth) acrylate resin. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 10. A black matrix comprising the cured product according to claim 11. The black matrix according to claim 12, wherein the optical density per 1 μm of the film thickness is 4.0 or more. An image display device produced by using the black matrix according to claim 12 or 13.

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