JP2022063445A - Photosensitive coloring composition, cured product, black matrix and image display device - Google Patents

Abstract

To provide a photosensitive coloring composition that has a high light-blocking performance even when formed into a thin film, and has sufficiently reduced unevenness in a dry state.SOLUTION: A photosensitive coloring composition contains (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, (d) a colorant, and (e) a solvent, the (e) solvent containing a solvent (e1) with a boiling point of 200-260°C at 760 mmHg and surface tension of 33 mN/m or more at 25°C. The photosensitive coloring composition is cured into a coating layer having optical density of 3.0 or more per 1.0 μm in a thickness.SELECTED DRAWING: Figure 1

Description

The present invention relates to a photosensitive coloring composition, a cured product, a black matrix (Black Matrix, hereinafter abbreviated as "BM"), and an image display device. In particular, it is suitable for a photosensitive coloring composition for BM, which is excellent in suppressing the occurrence of pin unevenness during hot plate drying.

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

Currently, a pigment dispersion method is known as a typical method for manufacturing a color filter. When a color filter is manufactured by the pigment dispersion method, a photosensitive coloring composition containing a black pigment such as carbon black is first applied onto a transparent substrate, dried under reduced pressure in a vacuum dryer, and then heated and dried in a hot plate. Then, after image exposure and development, BM is formed by curing (curing) by high temperature treatment of 200 ° C. or higher. Pixels are formed by repeating this for each color such as red, green, and blue to form a BM and a color filter having pixels. However, if the drying after coating progresses unevenly, the film thickness uniformity deteriorates and the BM In addition, there is a problem that unevenness occurs on the pixels.

The BM is generally arranged in a grid pattern, a stripe pattern, or a mosaic pattern between pixels of red, green, blue, etc., and has a role of improving contrast or preventing light leakage by suppressing color mixing between the pixels. .. Therefore, the BM is required to have a high light-shielding property. Further, since the edge portion of the pixels such as red, green, and blue formed after the BM is partially overlapped with the BM, a step is formed at the overlapped portion due to the influence of the film thickness of the BM. At this overlapping portion, the flatness of the pixels is impaired, non-uniformity of the liquid crystal cell gap or disorder of the orientation of the liquid crystal occurs, which causes a decrease in display capability. Therefore, in recent years, it has been particularly required to reduce the film thickness of the BM, and in order to exhibit sufficient light-shielding properties even when the film thickness is reduced, the concentration of the coloring material in the BM tends to increase, and the film thickness is not sufficient. Unevenness due to uniformity becomes particularly noticeable.

Against this background, there is a demand for a photosensitive coloring composition having excellent light-shielding properties even when the film is thinned and excellent in suppressing unevenness during drying. For example, Patent Documents 1 and 2 describe photosensitive coloring compositions containing a specific solvent.

Japanese Patent Application Laid-Open No. 2015-069098 Japanese Unexamined Patent Publication No. 2008-268894

When the present inventors performed a BM evaluation using the photosensitive coloring compositions described in Patent Documents 1 and 2, it was found that the suppression of unevenness during hot plate drying was not sufficient.

Therefore, an object of the present invention is to provide a photosensitive coloring composition which is excellent in light-shielding property even when thinned and excellent in suppressing unevenness during drying.

As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a specific solvent and having an optical density per unit film thickness of a certain level or more. That is, the gist of the present invention lies below.

[1] A photosensitive coloring composition containing (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, (d) a coloring material, and (e) a solvent.
The solvent (e) contains a solvent (e1) having a boiling point of 200 to 260 ° C. at 760 mmHg and a surface tension of 33 mN / m or more at 25 ° C.
A photosensitive coloring composition characterized in that the optical density per 1.0 μm film thickness of the cured coating film is 3.0 or more.

[2] The photosensitive coloring composition according to [1], wherein the solvent (e1) is 1,4-butanediol diacetate.
[3] The photosensitive coloring composition according to [1] or [2], wherein the content of the coloring material (d) with respect to the total solid content is 30% by mass or more.
[4] The photosensitive coloring composition according to any one of [1] to [3], wherein the coloring material (d) contains carbon black.

[5] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [4].
[6] A black matrix composed of the cured product according to [5].
[7] An image display device having the black matrix according to [6].

According to the present invention, it is possible to provide a photosensitive coloring composition having excellent light-shielding properties even when thinned and excellent in suppressing unevenness during drying.

It is sectional drawing which shows an example of the organic EL element provided with the color filter in 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 coloring composition or the ink described later.
In the present invention, the weight average molecular weight refers to the polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
Further, in the present invention, the "amine value" represents an amine value in terms of effective solid content, and is a value represented by the amount of base per 1 g of solid content of the dispersant and the equivalent mass of KOH, unless otherwise specified. Is. The measurement method will be described later.

[Photosensitive coloring composition]
The photosensitive coloring composition of the present invention contains (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, (d) a coloring material, and (e) a solvent, and (e). The solvent contains a solvent (e1) having a boiling point of 200 to 260 ° C. at 760 mmHg and a surface tension of 33 mN / m or more at 25 ° C., and the optical density per 1.0 μm of the cured coating film is 3.0 or more. Is.

The photosensitive coloring composition of the present invention may further contain a dispersant and thiols, and if necessary, an adhesion improver, a coatability improver, a pigment derivative, a development improver, and an ultraviolet absorber. , Antioxidants and the like may be contained, and it is preferable that each compounding component is used in a state of being dissolved or dispersed in an organic solvent.

<(A) Alkali-soluble resin>
The photosensitive coloring composition of the present invention contains (a) an alkali-soluble resin. (A) The alkali-soluble resin is particularly limited as long as the solubility of the exposed portion and the non-exposed portion in alkaline development changes after the coating film obtained by applying and drying the photosensitive coloring composition is exposed. Although not, it is preferably an alkali-soluble resin having a carboxy group. Further, those having an ethylenically unsaturated group are preferable, and an alkali-soluble resin having an ethylenically unsaturated group and a carboxy group is more preferable. Specific examples thereof include an epoxy (meth) acrylate resin having a carboxy group and an acrylic copolymer resin, and more specific examples thereof are (A1-1), (A1-2) and (A2-) described later. 1), (A2-2), (A2-3) and (A2-4) are mentioned, and these may use one kind or two or more kinds. Among the above, epoxy (meth) acrylate resins (A1-1) and (A1-2) having a carboxy group are particularly preferable.

When creating a color filter, a polymer resin having an acidic functional group such as a hydroxyl group, a carboxy 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 developing solution. To. Among these, a polymer resin having a carboxy 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 carboxy group, they easily react with the initiator, monomer, dispersant, and other additives having a basic group in the photosensitive coloring composition. , Storage stability may deteriorate.

Examples of the epoxy (meth) acrylate resin having a carboxy group include the following epoxy (meth) acrylate resin (A1-1) and / or epoxy (meth) acrylate resin (A1-2).

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

<Epoxy (meth) acrylate resin (A1-1) having a carboxy group and an ethylenically unsaturated group bond>
Examples of the epoxy resin as a raw material include bisphenol A type epoxy resin (for example, "jER (registered trademark; the same applies hereinafter) 828", "jER1001", "jER1002", "jER1004", etc.) manufactured by Mitsubishi Chemical Corporation, bisphenol. Epoxy obtained by the reaction of the alcoholic hydroxyl group of the 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, Mitsubishi). "JER807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Chemical Corporation), an epoxy resin obtained by the reaction of an alcoholic hydroxyl group of a bisphenol F type epoxy resin with epichlorohydrin (for example, Japan). "NER-7406" manufactured by Kayakusha (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 Resins (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Corporation), (o, m, p-) Cresol novolak type epoxy resin (for example, "EOCN (registered trademark. The same shall apply hereinafter) -102S", "EOCN-1020", "EOCN-104S") manufactured by Nippon Kayaku Co., Ltd., triglycidyl isocyanurate (for example). , Nissan Chemical Corporation "TEPIC (registered trademark)"), Trisphenol methane type epoxy resin (for example, "EPPN (registered trademark; the same shall apply hereinafter) -501", "EPPN-502" manufactured by Nippon Kayaku Co., Ltd., "EPPN-503"), alicyclic epoxy resin ("Ceroxide (registered trademark; the same shall apply hereinafter) 2021P" manufactured by Daicel Co., Ltd., "Ceroxyside EHPE"), and a phenol resin obtained by the reaction of dicyclopentadiene and phenol was glycidylated. Epoxy resins (for example, "EXA-7200" manufactured by DIC, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resins represented by the following general formulas (a1) to (a6), and the like are preferably used. be able to. Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (a1), and "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (a2). Examples of the epoxy resin represented by the following general formula (a4) include "NC-3000" and "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Corporation.

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

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

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

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

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

In the above general formula (a5), R ⁵¹ to R ⁵⁴ are each independently composed of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R ⁵⁵ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R ⁵⁶ is an alkylene group having 1 to 5 carbon atoms independently. be. k is an integer of 1 to 5, l is an integer of 0 to 13, and m is an integer of 0 to 5 independently.

In the above general formula (a6), n and o are independently integers of 1 to 9.
R ²³ 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 ^23s existing in one molecule may be the same or different from each other.

Among these, it is preferable to use the epoxy resin represented by any of the general formulas (a1) to (a6).

Examples of the α, β-unsaturated monocarboxylic acid ester having an α, β-unsaturated monocarboxylic acid or a carboxy 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 adipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) ) Acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) Acryloyloxybutylmaleic acid,
The (meth) acrylic acid ester is a single amount having one hydroxyl group at the end by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to (meth) acrylic acid. Body and
Alternatively, a monomer having one hydroxyl group at the end such as hydroxyalkyl (meth) acrylate, or a compound having one hydroxyl group at the end such as pentaerythritol tri (meth) acrylate, and (maleic) succinic acid, Examples thereof include (meth) acrylic acid esters having one or more ethylene unsaturated groups and one carboxy group at the end by adding an acid (anhydride) such as (anhydrous) phthalic acid and (maleic anhydride) maleic acid. .. In addition, (meth) acrylic acid dimer and the like can also be mentioned.

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

As the epoxy resin, α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxy 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 carboxy 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.
By setting the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxy group to the above lower limit or more, the amount of unsaturated group introduced becomes sufficient, and the subsequent polybasic acid And / or its reaction with the anhydride is sufficient, and there is a tendency that a large amount of residual epoxy group can be suppressed. On the other hand, by setting the amount to be used to the upper limit or less, it is possible to suppress the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxy group from remaining as an unreacted product. Tend.

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

Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic acid 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 carboxy group to an epoxy resin can be used. The desired product can be obtained by a continuous reaction under the same conditions as the addition reaction of the ester. The amount of the polybasic acid and / or its anhydride component added is preferably such that the acid value of the carboxy group-containing epoxy (meth) acrylate resin to be produced is in the range of 10 to 150 mgKOH / g, and further 20 It is preferably in the range of ~ 140 mgKOH / g. When it is at least the lower limit value, the alkali developability tends to be good, and when it is at most the upper limit value, the curability tends to be good.

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

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

The acid 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, more preferably 80 mgKOH / g or more, and 200 mgKOH. It is preferably / g or less, and more preferably 150 mgKOH / g or less. When it is at least the lower limit value, the developability tends to be good, and when it is at most the upper limit value, the alkali resistance tends to be good.

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, 2,000 or more is further preferable, and 2,300 or more is particularly preferable. Further, it is preferably 20,000 or less, more preferably 15,000 or less, further preferably 10,000 or less, further preferably 8,000 or less, and 6,000 or less. Is particularly preferable. When it is at least the above lower limit value, the sensitivity, coating film strength, and alkali resistance tend to be good, and when it is at least the above upper limit value, the developability and resolubility tend to be good. ..

<Acrylic copolymer resin (A2-1) (A2-2) (A2-3) (A2-4)>
Examples of the acrylic copolymer resin include JP-A-7-207211A, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, and Japanese Patent Publication No. Various polymer compounds described in JP-A-2000-563118, JP-A-2003-233179, JP-A-2007-270147, and the like can be used, but the following (preferably: Examples thereof include the resins A2-1) to (A2-4), and among them, the (A2-1) resin is particularly preferable.

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

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

The photosensitive coloring 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 coloring composition for color filters. For example, the alkali-soluble resins described in JP-A-2007-27172, JP-A-2007-316620, JP-A-2007-334290 and the like can be mentioned.

(A) The content of the alkali-soluble resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, based on the total solid content of the photosensitive coloring composition of the present invention. It is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, and particularly preferably 25% by mass or less. When it is set to the lower limit value or more, the solubility of the unexposed portion in the developing solution tends to be good, and when it is set to the upper limit value or less, excessive penetration of the developing solution into the exposed portion can be suppressed. It can be done, and the sharpness and adhesion of the image tend to be good.
As described above, the photosensitive coloring composition of the present invention is (a) an alkali-soluble resin as described above (A1-1), (A1-2), (A2-1), (A2-2). , (A2-3) and (A2-4) are preferably contained, and when other alkali-soluble resins are contained, the content ratio thereof is 20% by mass with respect to the total of (a) alkali-soluble resins. % Or less, preferably 10% by mass or less.

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

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

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propanetriacrylate, trimethylol ethanetriacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, and methacrylic acid esters in which the acrylates of these exemplary compounds are replaced with methacrylates. Similarly, an itaconic acid ester replaced with itaconate, a crotonic acid ester replaced with clonate, a maleic acid ester replaced with maleate, and the like can be mentioned.

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

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

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

In the above formulas (b1) to (b4), R ^b is a group represented by the following general formula (b5), and in the above formula (b3), R ⁸ is an alkyl group having 1 to 6 carbon atoms. In b4), 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. The plurality of ^R9s existing in one molecule may be the same or different from each other.

In the above formula (b5), R ⁶ represents an alkylene group in which the main chain may have branches having 2 to 6 carbon atoms, and R ⁷ represents a hydrogen atom or a methyl group. m represents an integer of 0 to 3. When m is 2 or 3, the plurality of ^R6s 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. Below, 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, but 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, but 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 carbon number of the arylene alkylene group of R ⁹ is preferably 7 or more, and preferably 9 or less from the viewpoint of adhesion to the substrate. Examples of the arylene alkylene group having 7 to 10 carbon atoms include a 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, ^R9 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 having 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.

In the general formula (b5), m represents an integer of 0 to 3. The general formulas (b1) to (b4) include a plurality of R ^b groups, but the R ^b groups may be the same or different. From the viewpoint of adhesion to the substrate, it is preferable that the R ^{bs are different from each other, and it is more preferable that the R b groups} have different m. Specifically, an R ^b group having m of 0 (hereinafter abbreviated as R ^b1 group) and an integer R ^b group having m of any one of 1 to 3 (hereinafter abbreviated as R ^b2 group) are designated. 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 group, and at least two are more preferably R ^b2 group.
Of the plurality of R ^b groups contained in the general formula (b2), it is preferable that at least one is an R ^b2 group, and it is more preferable that at least two are R ^b2 groups.
Of the plurality of R ^b groups contained in the general formula (b3), at least one is preferably R ^b2 group, and at least two are more preferably R ^b2 group.
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.

Among these, from the viewpoint of adhesion to the substrate, it is preferable that the (b) photopolymerizable monomer contains a compound having the following structure.

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

<(C) Photopolymerization Initiator>
The photosensitive coloring composition of the present invention contains (c) a photopolymerization initiator. 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.

As the photopolymerization initiator, for example, a metallocene compound containing a titanosen compound described in JP-A-59-152396 and JP-A-61-151197; a hexaarylbi described in JP-A-2000-56118. Imidazole derivatives; N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-phenylglycine, etc. described in JP-A No. 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 titanocene derivatives, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro) Pheni-1-yl), Dicyclopentadienyl Titanium Bis (2,3,5,6-Tetrafluoropheni-1-yl), Dicyclopentadienyl Titanium Bis (2,4,6-Trifluorophenyl) 1-yl), dicyclopentadienyl titanium di (2,6-difluoropheni-1-yl), dicyclopentadienyl titanium di (2,4-difluoropheni-1-yl), di (methylcyclopenta) Dienyl) Titanium bis (2,3,4,5,6-pentafluoropheni-1-yl), Di (methylcyclopentadienyl) Titanium bis (2,6-difluoropheni-1-yl), Dicyclo Examples thereof include pentadienyl titanium [2,6-di-fluoro-3- (pyro-1-yl) -pheni-1-yl].

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

Examples of 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) Butane-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4 -Dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like can be mentioned.

As the photopolymerization initiator, oxime derivatives (oxime ester compounds and ketooxime ester compounds) are particularly effective in terms of sensitivity, and when an alkali-soluble resin containing a phenolic hydroxyl group is used, the point of sensitivity is particularly high. Oxime derivatives (oxime ester-based compounds and keto-oxime-based compounds) having such excellent sensitivity are particularly useful. Among the oxime derivatives, oxime ester compounds are particularly preferable from the viewpoint of adhesion to the substrate.
The photopolymerization initiator of an oxime ester compound 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 in a small amount and has a thermal reaction. It is possible to design a photosensitive coloring composition that is stable and highly sensitive in a small amount. In particular, in the case of an oxime ester-based compound containing a optionally substituted carbazolyl group (a group having a optionally substituted carbazole ring) from the viewpoint of light absorption of an exposure light source for i-ray (wavelength 365 nm). , This structural property is well expressed and is more preferable. Currently, the market demands a thin film BM (black matrix) with a high degree of shading, and the pigment concentration is also increasing. It is especially effective in such situations.

Examples of the oxime ester compound include a compound containing a structural portion represented by the following general formula (22), and preferably an oxime ester 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. Cyclo alkanoyl group of 3 to 8, alkoxycarbonyl alkanoyl group of 3 to 20 carbon atoms, phenoxycarbonyl alkanoyl group of 8 to 20 carbon atoms, heteroallyloxycarbonyl alkanoyl group of 3 to 20 carbon atoms, 2 to 10 carbon atoms An aminoalkylcarbonyl group, an aryloyl group having 7 to 20 carbon atoms, a heteroarylloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms is shown.

(In the formula (23), R ^21a is 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 with hydrogen, 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, alkalinoyl 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.

In addition, 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 composed of a combination thereof can be mentioned. In addition, 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 of.

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 carbazolyl 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, one containing a carbazolyl 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, and a heteroaryl group having 5 to 25 carbon atoms which may be substituted, substituted. 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 carbazolyl 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 carbazolyl group.

Commercially available products of such an oxime ester photopolymerization initiator include OXE-02 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Joshu 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.

Examples of the ketooxime ester compound include a compound containing a structural portion represented by the following general formula (24), and preferably a ketooxime 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 with 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 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.

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 composed of a combination thereof can be mentioned. In addition, 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. A heteroallyloyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an alkylamino 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 allyloyl 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, 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 a ketooxime ester photopolymerization initiator include OXE-01 manufactured by BASF, TR-PBG-305 manufactured by Joshu Strong Electronics Co., Ltd., and the like.

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-butylanthraquinone 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 Acetphenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanol, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy Acetphenone 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) acrydin; phenazine derivatives such as 9,10-dimethylbenzphenazine. ; Anthron derivatives such as benzansuron may also be mentioned.
Among these photopolymerization initiators, oxime ester derivatives are particularly preferable for the above-mentioned reasons.

<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 the xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, and the coumarin dyes having a heterocycle described in JP-A-3-239703 and JP-A-5-289335. , JP-A-3-239703, 3-Ketokumarin compound described in JP-A-5-289335, pyrromethene dye described in JP-A-6-19240, and others, JP-A-47-2528, JP-A-54- 155292, Japanese Patent Publication No. 45-373777, Japanese Patent Application Laid-Open No. 48-84183, Japanese Patent Application Laid-Open No. 52-112681, 58-15503, 60-88005, 59-56403, Japanese Patent Laid-Open No. Dyes having a dialkylaminobenzene skeleton described in Kaihei 2-69, JP-A-57-16888, JP-A-5-107761, JP-A-5-210240, JP-A-4-288818. Can be mentioned.

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

(C) The content of the photopolymerization initiator is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably, with respect to the total solid content of the photosensitive coloring composition of the present invention. Is 4% by mass or more, usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and particularly preferably 8% by mass or less. When it is set to the lower limit value or more, the sensitivity tends to be improved, and when it is set to the upper limit value or less, the solubility of the unexposed portion in the developer tends to be improved.

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

<(D) Color material>
The photosensitive coloring composition of the present invention contains (d) a coloring material. The coloring material refers to a material that colors the photosensitive coloring composition of the present invention. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like.

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

Specific examples of pigments that can be used in the present invention are shown below by pigment numbers. The terms such as "CI Pigment Red 2" listed below mean the color index (CI).
As the red pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 can be mentioned. Among these, preferably C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, 254 can be mentioned.

As the blue pigment, C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned. Among these, preferably C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 60, more preferably C.I. I. Pigment Blue 15: 6, 60 can be mentioned.

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

As the yellow pigment, C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,41,42,43,48,53,55,61,62,62: 1,63,65,73,74,75,81,83,87,93,94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 can be mentioned. Among these, preferably C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.

As the orange pigment, C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 can be mentioned. Among these, preferably, C.I. I. Pigment Orange 38, 64, 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, 29 More preferably C.I. I. Pigment Violet 23, 29 can be mentioned.

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

Further, regarding other pigments that can be mixed and used, C.I. I. Indicated by number, for example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, 64, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Brown pigments 23, 25, 26 and the like can be mentioned.

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

Made by Mitsubishi Chemical Corporation: MA7, MA77, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350 , # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B
Made by Degusa: Printex (registered trademark; the same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexA, PrintexA. U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color
Black S170
Manufactured by Cabot Corporation: Monarch (registered trademark; the same applies hereinafter) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark. REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN® XC72R, ELFTEX®-8
Made by Biller: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN10URA RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

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

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

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

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

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

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 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 can be mentioned.

The photosensitive coloring 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 to form a black matrix, (d) use a black color material such as carbon black or titanium black described above, or mix multiple types of color materials other than black and adjust to black. Just do it. Among them, it is particularly preferable to use carbon black from the viewpoint of dispersion stability and light-shielding property.

The photosensitive coloring composition of the present invention is highly effective in a region where the concentration of the coloring material is high. Especially in recent years, it is necessary to increase the density of the coloring material in order to increase the degree of shading. The content ratio of the coloring material in the region where the effect is large is 30% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more, based on the total solid content of the photosensitive coloring composition. Is more preferable, and 52% by mass or more is particularly preferable. Further, from the viewpoint of image forming performance, 70% by mass or less is preferable, and 65% by mass or less is more preferable.

In the photosensitive coloring composition of the present invention, when the content ratio of the coloring material is within the above range, a photosensitive coloring composition having a high light-shielding property (optical density, OD value) can be obtained. Specifically, (d) by setting the content of the coloring material to 30% by mass or more, the optical density when a black matrix having a thickness of 1.0 μm is formed using the photosensitive coloring composition of the present invention can be measured. It can be a value of 3.0 or more. The optical density is more preferably 3.5 or more, further preferably 4.0 or more, and particularly preferably 4.2 or more. In the region where the light-shielding property is high, unevenness during heating and drying using a hot plate is easily observed, but when the photosensitive coloring composition of the present invention is used, especially when the content ratio of (d) the coloring material is large, it is easy to observe. The effect of suppressing unevenness of the present invention can be confirmed well.

In the photosensitive coloring composition, the content ratio of (d) the coloring material is not particularly limited, but (a) is usually 20 parts by mass or more, preferably 30 parts by mass or more, more preferably per 100 parts by mass of the alkali-soluble resin. Is 40 parts by mass or more, more preferably 60 parts by mass or more, still more preferably 80 parts by mass or more, particularly preferably 120 parts by mass or more, most preferably 160 parts by mass or more, and usually 500 parts by mass or less, preferably 500 parts by mass or more. It is 300 parts by mass or less, more preferably 280 parts by mass or less. (D) When the content ratio of the coloring material is set to the lower limit value or more, it tends to be easy to suppress the decrease in the solubility of the unexposed portion in the developing solution, and when it is set to the upper limit value or less, the adhesion during development tends to be suppressed. There is a tendency for sex to improve.

<Dispersant>
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 thereof in order to ensure the stability of quality.
As the dispersant, a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxy group; a phosphate group; a sulfonic acid group; or these groups; a primary, secondary or tertiary amino group. A quaternary ammonium base; a polymer dispersant having a functional group such as a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is preferable. Among them, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine is particularly preferable. By using a polymer dispersant having these basic functional groups, the dispersibility can be improved and a high light-shielding property tends to be achieved.

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

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

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

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less, and more preferably 30,000 or less. By setting the value to the upper limit or less, the alkali developability tends to be good even when the pigment concentration is high.
Examples of the urethane-based and acrylic 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 preferable as the urethane-based polymer dispersant having the above-mentioned basic functional group and having a polyester and / or a polyether bond and having a weight average molecular weight of 30,000 or less.

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

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

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

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

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

Polyester ester diols are those obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, such as poly (poly). Oxytetramethylene) adipate and the like. The most preferable polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

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

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

The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.
A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described. Examples of active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, include a hydrogen atom in a functional group such as a hydroxyl group, an amino group and a thiol group, and among them, an amino group, particularly a first-class one. 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 indole 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, benzothiasiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, aclysine ring, isoquinoline ring and other nitrogen-containing hetero 6-membered ring. Ring is mentioned. Of these nitrogen-containing heterocycles, the imidazole ring or the triazole ring is preferable.

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

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

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

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

<Measuring method of amine value>
The tertiary amine value of the dispersant is expressed by the amount of base per 1 g of solid content excluding the solvent in the dispersant sample and the equivalent amount of KOH, and can be measured by the following method.
Weigh 0.5-1.5 g of the dispersant sample into 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 formula with the inflection point of the titration pH curve as the titration end point.

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

When the isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time is improved.
The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. Especially, 30,000 or less is preferable. When it is at least the above lower limit value, the dispersibility and dispersion stability tend to be good, and when it is at least the above upper limit value, the solubility tends to be good. 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).

The content of the dispersant is usually 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, usually 1% by mass or more, preferably 3% by mass, based on the total solid content of the photosensitive coloring composition. As mentioned above, it is more preferably 5% by mass or more, further preferably 7% by mass or more, and particularly preferably 10% by mass or more. The content ratio of the dispersant is usually 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and usually 200 parts by mass or less with respect to 100 parts by mass of the coloring material (d). It is preferably 80 parts by mass or less, more preferably 50 parts by mass or less. When it is set to the lower limit value or more, it tends to be easy to secure sufficient dispersibility, and when it is set to the upper limit value or less, the color density, sensitivity, film forming property, etc. are improved without reducing the ratio of other components. It tends to be sufficient.

<(E) Solvent>
The photosensitive coloring composition of the present invention comprises (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, (d) a coloring material, and various materials used as necessary. (E) Used in a state of being dissolved or dispersed in a solvent.

<(E1) Solvent>
The solvent (e) in the present invention has a boiling point (pressure of 760 mmHg condition; hereinafter, all the same applies to the boiling point) of 200 to 260 ° C. and a surface tension (condition of a temperature of 25 ° C., all the same applies to the surface tension) of 33 mN. Contains a solvent (e1) of / m or more.

From the viewpoint of suppressing unevenness during hot plate drying, the boiling point is more preferably 210 ° C. or higher, further preferably 215 ° C. or higher, particularly preferably 220 ° C. or higher, and most preferably 225 ° C. or higher. From the viewpoint of adhesion during development, the boiling point is more preferably 250 ° C. or lower, further preferably 245 ° C. or lower, particularly preferably 240 ° C. or lower, and most preferably 235 ° C. or lower.

From the viewpoint of suppressing unevenness during hot plate drying, the surface tension is more preferably 33.5 mN / m or more, and more preferably 34.0 mN / m or more.

Examples of such a solvent (e1) include 1,4-butanediol diacetate, 1,6-hexanediol diacetate, triacetin, and 1,3-butylene glycol. From the viewpoint of suppressing unevenness during hot plate drying, 1,4-butanediol diacetate is preferable.

(E) The ratio of the solvent (e1) in the solvent is not particularly limited, but from the viewpoint of suppressing unevenness during hot plate drying, 0.1% or more is preferable, 1% or more is more preferable, and 2% or more is further preferable. 3% or more is particularly preferable, and 5% or more is most preferable. Further, from the viewpoint of adhesion during development, 80% or less is preferable, 60% or less is more preferable, 40% or less is further preferable, 20% or less is particularly preferable, and 10% or less is most preferable.

<Other solvents>
The solvent (e) in the present invention may contain other solvents in addition to the solvent (e1) for the purpose of adjusting the sensitivity, development adhesion and coatability of the photosensitive coloring composition.
Examples of other solvents include the following.

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

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

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

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

Halogenated hydrocarbons such as butyl chloride, amilk chloride;
Etheretones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile;

Examples of commercially available solvents corresponding to the above include Mineral Spirit, Barsol # 2, Apco # 18 Solvent, Apco Thinner, and Sokal Solvent No. 1 and No. 2. Solvento # 150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve (“Cellosolve” is a registered trademark; the same shall apply hereinafter), Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglime (any of them). Also the product name) and so on.

These solvents may be used alone or in combination of two or more.
Of the above solvents, glycol alkyl ether acetates and glycol monoalkyl ethers are preferable, and glycol alkyl ethers are preferable, because they have a good balance of coatability and development adhesion, and the solubility of the constituent components in the composition is relatively high. Acetates are more preferred. Of these, propylene glycol monomethyl ether and 3-methoxybutyl acetate are particularly preferable because of the solubility of the constituents in the composition.

In the photosensitive coloring composition of the present invention, the content ratio of the solvent is not particularly limited, but from the viewpoint of suppressing unevenness during hot plate drying and coatability, the total solid content in the photosensitive coloring composition is preferably 5% by mass. The above is more preferably 8% by mass or more, further preferably 10% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and particularly preferably 20% by mass or less. Is.

<Other ingredients of the photosensitive coloring composition>
In addition to the above-mentioned components, the photosensitive coloring composition of the present invention may appropriately contain thiols, adhesion improvers, coatability improvers, pigment derivatives, development improvers, ultraviolet absorbers, antioxidants and the like. can.

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

When thiols are used, the content ratio of thiols is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably, with respect to the total solid content of the photosensitive coloring composition of the present invention. Is 0.5% by mass or more, usually 10% by mass or less, preferably 5% by mass or less. When it is set to the lower limit value or more, the sensitivity decrease tends to be suppressed, and when it is set to the upper limit value or less, the storage stability tends to be improved.

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

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

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

The content ratio of the adhesion improver in the photosensitive coloring composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.10% by mass or more, and 0. It is more preferably .50% by mass or more, more preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and further preferably 2.0% by mass or less. It is preferably 1.5% by mass or less, and particularly preferably 1.5% by mass or less. When it is at least the lower limit value, the adhesion tends to be improved, and when it is at least the upper limit value, the developability tends to be good.

<Applicability improver>
In order to improve the coatability, the photosensitive coloring composition of the present invention may contain a surfactant as a coatability improver. As the surfactant, for example, various kinds such as anionic type, cationic type, nonionic type and amphoteric surfactant can be used. Among them, it is preferable to use a nonionic surfactant because it is unlikely to adversely affect various properties, and among them, a fluorine-based or silicone-based surfactant is effective in terms of coatability.

Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by Big Chemie), and KP340. (Manufactured by Shinetsu Silicone), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Toray Dow Corning), DS-401 (manufactured by Daikin) , L-77 (manufactured by Nippon Unicar), FC4430 (manufactured by 3M Japan) and the like. As the surfactant, one type may be used, or two or more types may be used in combination in any combination and ratio.

The content ratio of the surfactant in the photosensitive coloring composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 0.05% by mass or more in the total solid content. , 1.0% by mass or less, more preferably 0.7% by mass or less, further preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less. preferable. When the value is not less than the lower limit, the resist coating uniformity tends to be improved, and when the value is not more than the upper limit, the resist sensitivity tends not to be lowered.

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

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

The blending ratio of the pigment derivative is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more with respect to the total solid content of the photosensitive coloring composition. It is preferable, and it is preferably 10% by mass or less, more preferably 5% by mass or less. When it is at least the lower limit value, the dispersion stability tends to be improved, and when it is at least the upper limit value, the developability tends to be good.

<Physical characteristics of the photosensitive coloring composition>
The photosensitive coloring composition of the present invention can be suitably used for forming a black matrix, and from such a viewpoint, it is preferably black. Further, the optical density (OD) per 1.0 μm film thickness of the cured coating film is 3.0 or more. It is more preferably 3.5 or more, further preferably 4.0 or more, particularly preferably 4.2 or more, and usually 6.0 or less. By setting the value to the lower limit or more, there is a tendency that sufficient light-shielding property can be ensured.
The optical density means a transmission optical density in which the spectral sensitivity characteristic of the light receiving portion is indicated by ISO visual density in the ISO 5-3 standard. Usually, as the light source, the A light source specified by the CIE (Commission Internationale de l'Eclairage) is used. As a measuring instrument that can be used for measuring the transmitted optical density, for example, X-Rite 361T (V) manufactured by Sakata Inx Corporation can be mentioned.

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

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

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

[Cursed product]
A cured product can be obtained by curing the photosensitive coloring composition of the present invention. The cured product obtained by curing the photosensitive coloring composition can be suitably used as a member constituting a color filter such as a pixel, a black matrix or a coloring spacer.

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

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

For the support, in order to improve the surface physical properties such as adhesiveness, if necessary, corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc. May be done.
The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. When the thin film forming treatment of various resins is performed, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

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

(3) Formation of Black Matrix (3-1) Application of Photosensitive Coloring Composition The application of the photosensitive coloring 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. It is preferable from.

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. be. By setting the value to the upper limit or less, pattern development tends to be easy, and gap adjustment in the liquid crystal cell formation step tends to be easy. By setting the value to the lower limit or more, the desired color expression tends to be facilitated.

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

The higher the drying temperature, the better the adhesiveness of the coating film to the transparent substrate, but if it is too high, the alkali-soluble resin may be decomposed, inducing thermal polymerization and causing development failure. Further, if the drying progresses non-uniformly, the film thickness uniformity deteriorates and unevenness occurs.

(3-3) Exposure Image exposure is performed by superimposing a negative mask pattern on a coating film of a photosensitive coloring composition and irradiating light having a wavelength from the ultraviolet region to the visible region through the mask pattern. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film. The light source used for the above image exposure is not particularly limited. Examples of the light source include a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, and a carbon arc. An optical filter can also be used when irradiating light of a specific wavelength for use.

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

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

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

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

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

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

[Colored spacer]
The photosensitive coloring composition of the present invention can also be used as a resist for a coloring spacer in addition to the black matrix. When the spacer is used for the TFT type LCD, the TFT may malfunction as a switching element due to the light incident on the TFT, and the colored spacer is used to prevent this. For example, Japanese Patent Application Laid-Open No. 8-234212. 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 forms a transparent electrode such as ITO on an image in this state and is used as a part of parts such as a color display and a liquid crystal display device, but the surface is smooth. If necessary, a top coat layer such as polyamide or polyimide can be provided on the image in order to improve the properties and durability. Further, in some applications such as a plane alignment type drive system (IPS mode), a transparent electrode may not be formed.

[Image display device]
The image display device of the present invention has a cured product obtained by curing the photosensitive coloring composition of the present invention, and is not particularly limited as long as it is a device for displaying an image or an image, but is a liquid crystal display device described later. And organic EL display.

[Liquid crystal display device]
The liquid crystal display device of the present invention has 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.

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

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

The gap for bonding to the facing substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After bonding to the facing substrate, the parts other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then depressurized in a vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the inside of the chamber leaks to inject the liquid crystal into the liquid crystal cell. .. The degree of decompression in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ^-7 Pa, but preferably 1 × 10 ^-3 to 1 × 10 ^-6 Pa. Further, it is preferable to heat the liquid crystal cell at the time of depressurization, and the heating temperature is usually 30 to 100 ° C, more preferably 50 to 90 ° C. The warming retention at the time of depressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal display. A liquid crystal display device (panel) is completed by sealing the liquid crystal cell into which the liquid crystal is injected by curing the UV curable resin and sealing the liquid crystal injection port.

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

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

When an organic EL display is manufactured using the color filter of the present invention, for example, as shown in FIG. 1, a pattern formed by a photosensitive coloring composition (that is, pixels 20 and adjacent to it) is first placed on a transparent support substrate 10. A color filter in which a resin black matrix (not shown) provided between the pixels 20 is formed is produced, and an organic illuminant 500 is formed on the color filter via an organic protective layer 30 and an inorganic oxide film 40. The organic EL element 100 can be manufactured by laminating the above. At least one of the pixel 20 and the resin black matrix was produced by using the photosensitive coloring composition of the present invention. As a method of laminating the organic illuminant 500, a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter, or Examples thereof include a method of bonding the organic light emitter 500 formed on another substrate onto the inorganic oxide film 40. Using the organic EL element 100 thus produced, for example, the method described in "Organic EL Display" (Ohmsha, August 20, 2004, Luminous, Shizushi Tokito, Chihaya Adachi, Hideyuki Murata), etc. , An organic EL display can be manufactured.

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

Next, the present invention will be described in more detail with reference to synthetic examples, examples and comparative examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
The constituents of the photosensitive coloring composition used in the following Examples and Comparative Examples are as follows.

<Synthesis Example 1: Synthesis of Alkali Soluble Resin-II>

240 parts by mass of an epoxy compound (epoxy equivalent 264) having the above structure, 68.3 parts by mass of acrylic acid, 263.1 parts by mass of methoxybutyl acetate, 6.4 parts by mass of triphenylphosphine, and 0.16 parts by mass of paramethoxyphenol. The mixture was placed in a flask equipped with a thermometer, a stirrer and a cooling tube, and reacted at 90 ° C. for 12 hours until the acid value became 5 mgKOH / g or less.
Next, 19.0 parts by mass of trimethylolpropane (TMP), 100.0 parts by mass of biphenyltetracarboxylic acid dianhydride (BPDA), and 68.9 parts by mass of tetrahydrophthalic acid anhydride (THPA) were added to the reaction solution obtained by the above reaction. The mass part was placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react. An alkali-soluble resin-II of Mw) 4000 was obtained.

<Synthesis Example 2: Synthesis of Alkali Soluble Resin-III>

240 parts by mass of an epoxy compound (epoxy equivalent 264) having the above structure, 81.6 parts by mass of methacrylic acid, 263.1 parts by mass of methoxybutyl acetate, 6.4 parts by mass of triphenylphosphine, and 0.16 parts by mass of paramethoxyphenol. The mixture was placed in a flask equipped with a thermometer, a stirrer and a cooling tube, and reacted at 90 ° C. for 12 hours until the acid value became 5 mgKOH / g or less.
Next, 8.3 parts by mass of trimethylolpropane (TMP), 80.7 parts by mass of biphenyltetracarboxylic acid dianhydride (BPDA), and 51.6 parts by mass of tetrahydrophthalic acid anhydride (THPA) were added to the reaction solution obtained by the above reaction. The mass part was placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react. An alkali-soluble resin-III of Mw) 2500 was obtained.

The constituents of the photosensitive coloring composition used in the following Examples and Comparative Examples are as follows.
<Color material (pigment)>
R1060: "RAVEN1060" manufactured by BIRLA CARBON (carbon black)
R1080: "RAVEN1080" manufactured by BIRLA CARBON (carbon black)
<Dispersant>
BYK167: "DISPERBYK-167" manufactured by Big Chemie (urethane-based polymer dispersant)
<Dispersion aid>
S12000: "S12000" manufactured by Lubrizol (acidic derivative of phthalocyanine)
<Alkali-soluble resin>
Alkali-soluble resin-I: Epoxy acrylate resin of "WR-301" manufactured by ADEKA (weight average molecular weight (Mw) = 5700, solid acid value = 100 mgKOH / g)
Alkali-soluble resin-II: Resin described in Synthesis Example 1 Alkali-soluble resin-III: resin described in Synthesis Example 2 <photopolymerizable monomer>
PE-4A: "Light Acrylate PE-4A" manufactured by Kyoeisha Chemical Co., Ltd. (polyfunctional acrylate)
DPCA-20: "KAYARAD DPCA-20" manufactured by Nippon Kayaku Co., Ltd. (polyfunctional acrylate)
<Photopolymerizable initiator>
TR-PBG-304: "TR-PBG-304" (oxime ester) manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.
<Adhesion improver>
PM21: "KAYAMER PM21" manufactured by Nippon Kayaku Co., Ltd. (phosphoric acid-based monomer)
X-12-1048: "X-12-1048" manufactured by Shin-Etsu Chemical Co., Ltd. (polyfunctional acrylic silane)
<Surfactant>
F-554: "Megafuck F554" manufactured by DIC (fluorine-based surfactant)
F-559: DIC Corporation "Megafuck F559" (fluorine-based surfactant)
<Solvent>
PGMEA: Propylene Glycol Methyl Ether Acetate MBA: 3-Methoxybutyl Acetate 1,4-BDDA: 1,4-Butanediol Diacetate 1,3-BGDA: 1,3-butylene Glycol Diacetate Table 1 shows each solvent at 760 mmHg. The values of boiling point and surface tension at 25 ° C are shown.

<Preparation of dispersion-I and dispersion-II>
The pigments, dispersants, dispersion aids, alkali-soluble resins and solvents shown in Table 2 were mixed so as to have the mass ratios shown in Table 2 to obtain a mixed solution. The blending ratio of the solvent in Table 2 also includes the amounts of the dispersant, the dispersion aid, and the solvent derived from the alkali-soluble resin.
This mixed solution was dispersed with a paint shaker in the range of 25 to 45 ° C. for 3 hours. As the beads, 0.5 mmφ zirconia beads were used, and a mass 2.5 times that of the dispersion was added. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare dispersion-I and dispersion-II.

<Preparation of photosensitive coloring composition>
[Example 1 and Comparative Examples 1 and 2]
Using the above-prepared dispersion-I and dispersion-II, add each component so that the ratio of the solid content of each component in the total solid content is the blending ratio shown in Table 3, and further add the components to the photosensitive coloring composition. Each solvent was added so that the solvent ratio of the above was as shown in Table 3 and the content ratio of the total solid content was 14% by mass, and the mixture was stirred and dissolved to prepare a photosensitive coloring composition. Each of the obtained photosensitive coloring compositions was evaluated by the method described later.

(Evaluation of photosensitive coloring composition)
<Measurement of optical density (unit OD value) per unit film thickness>
The photosensitive coloring composition is applied onto a glass substrate with a spin coater so that the film thickness after heat curing is 1.1 μm, dried under reduced pressure at 100 Pa for 30 seconds, and then dried on a hot plate at 110 ° C. for 120 seconds. bottom. The obtained coating film was subjected to full-scale exposure treatment so that the exposure amount was 50 mJ / cm ² using ultraviolet rays having an intensity of 45 mW / cm ² at a wavelength of 365 nm without using a mask.
Subsequently, using a developer consisting of a 0.04 mass% KOH (potassium hydroxide) aqueous solution, shower development at 23 ° C. and a water pressure of 0.05 MPa was performed for 60 seconds, then development was stopped with pure water, and the mixture was washed with water. It was washed with a spray. The substrate was heat-cured (post-baked) at 230 ° C. for 30 minutes in an oven to obtain a substrate for optical density measurement.

The optical density (OD) of the obtained substrate was measured with a transmission densitometer (361T (V) manufactured by X-Rite), and the film thickness was measured with a scanning white interference microscope (VS1530 manufactured by Hitachi High Technology). The optical density (unit OD value, OD / μm) per unit film thickness (1.0 μm) was calculated from the optical density (OD) and the film thickness, and is shown in Table 3. The OD value is a numerical value indicating the light-shielding ability, and the larger the value is, the higher the light-shielding property is.

<Evaluation of pin unevenness when the hot plate is dried>
The photosensitive coloring composition was applied onto a glass substrate with a spin coater so that the film thickness after heat curing was 1.1 μm, and dried under reduced pressure at 100 Pa for 30 seconds to obtain a sample (glass substrate / coating film). .. The sample was placed on a columnar metal pin (diameter 1 cm, height 1 cm) placed on a hot plate so that the metal pin was in contact with the glass substrate side, and dried at a hot plate temperature of 110 ° C. for 120 seconds. The presence or absence of traces of metal pins on the surface of the coating film was visually confirmed.
〇: Metal pin marks cannot be confirmed ×: Metal pin marks can be confirmed

From the examples shown in Table 3, the optical density per unit film thickness (unit OD value, OD / μm) is a large value of 4.3, and the photosensitive coloring composition of the present invention is thinned even when it is thinned. It can be seen that the light blocking effect is excellent.
Further, from Examples 1 and Comparative Examples 1 and 2 shown in Table 3, the photosensitive property is characterized by containing a solvent having a boiling point of 200 to 260 ° C. at 760 mmHg and a surface tension of 33 mN / m or more at 25 ° C. It can be seen that the use of the coloring composition makes it possible to suppress the occurrence of pin unevenness during hot plate drying.
Since the temperature of the part where the metal pin contacts becomes high when the hot plate is dried, the coating film becomes easier to heat-flow compared to the part where the metal pin does not contact, and as a result of the uneven heat flow of the coating film, the pin There is a tendency for traces to remain. However, it is considered that no pin marks were generated because the heat flow was suppressed even at a high temperature by using a solvent having a large surface tension. In particular, by using a solvent having a high boiling point, the solvent does not vaporize during vacuum drying before the hot plate drying step, so that the effect of suppressing heat flow is considered to be remarkable.
In the photosensitive coloring composition shown in Comparative Example 2, the surface of the coating film was whitened after drying under reduced pressure. It is considered that this is because the photosensitive coloring composition contains only a solvent having a low boiling point, so that bumping or non-uniform evaporation occurs during drying under reduced pressure.

Claims (7)

A photosensitive coloring composition containing (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, (d) a coloring material, and (e) a solvent.
The solvent (e) contains a solvent (e1) having a boiling point of 200 to 260 ° C. at 760 mmHg and a surface tension of 33 mN / m or more at 25 ° C.
A photosensitive coloring composition characterized in that the optical density per 1.0 μm film thickness of the cured coating film is 3.0 or more. The photosensitive coloring composition according to claim 1, wherein the solvent (e1) is 1,4-butanediol diacetate. The photosensitive coloring composition according to claim 1 or 2, wherein the content of the coloring material (d) with respect to the total solid content is 30% by mass or more. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the coloring material (d) contains carbon black. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 4. A black matrix comprising the cured product according to claim 5. The image display device having the black matrix according to claim 6.

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