JP5454571B2 - Coloring composition, color filter and color liquid crystal display element - Google Patents

Description

  The present invention relates to a colored composition, a color filter, and a color liquid crystal display element, and more particularly, formation of a colored layer useful for a color filter used in a transmissive or reflective color liquid crystal display device, a color imaging tube element, and the like. The present invention relates to a colored composition used in the present invention, a color filter including a colored layer formed using the colored composition, and a color liquid crystal display device including the color filter.

  As a method of forming a color filter using a colored radiation-sensitive composition, a coating film of a colored radiation-sensitive composition is formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed, and a predetermined pattern is formed. A method of obtaining pixels of each color by irradiating radiation (hereinafter referred to as “exposure”) through a photomask having, developing and dissolving and removing unexposed portions, and then post-baking (Patent Document 1 and 2) is known. A method of forming a black matrix using a photopolymerizable composition containing a black material (Patent Document 3) is also known.

  And in the technical field of color filters in recent years, it has become mainstream to reduce the exposure amount to shorten the tact time, and has sufficient development resistance, solvent resistance, etc. even at a low exposure amount, that is, a colored layer. There is a demand for higher sensitivity of the radiation-sensitive composition for forming. In particular, regarding solvent resistance, problems such as occurrence of cracks and chips in the pixel pattern and elution of colored components from the pixel pattern are becoming apparent, and it is required to solve them. In order to meet the recent demands for high contrast, high brightness, and high color purity for color liquid crystal display elements, many of the pigments used in colored radiation-sensitive compositions have been made finer. It is considered that the treatment and surface treatment are performed, and the content ratio of the pigment in the colored radiation-sensitive composition tends to be higher.

  On the other hand, in patent document 4, in order to improve the chemical resistance of the colored layer formed using a coloring composition, it is proposed to contain a melamine resin etc. as a crosslinking agent. However, such a coloring composition has a problem that sufficient development resistance and solvent resistance cannot be obtained when the exposure amount is low or a specific pigment is used.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2007-225717 A

An object of the present invention is to provide a coloring composition that can form a pixel and a black matrix having sufficient development resistance even at a low exposure amount and having excellent solvent resistance.
Another object of the present invention is to provide a color filter having pixels formed from the colored composition, and a color liquid crystal display device comprising the color filter.

  As a result of intensive studies, the present inventors have incorporated a crosslinking agent having a specific structure in which an oxiranyl group, an oxetanyl group or a group having a polymerizable unsaturated bond is bonded via an aminomethyloxy structure into the colorant and the binder resin. As a result, the inventors have found that the above problems can be solved, and have completed the present invention.

  That is, the present invention relates to (A) a colorant, (B) a binder resin, and (C) a compound having a structure represented by the following formula (1) (hereinafter these are collectively referred to as “specific crosslinking agent”. A coloring composition characterized in that it contains a pigment).

(In the formula (1), X represents a group having an oxiranyl group, a group having an oxetanyl group or a group having a polymerizable unsaturated bond, and “*” represents a bond.)

The present invention also provides a color filter comprising a colored layer formed using the colored composition, and a color liquid crystal display device comprising the color filter.
The “colored layer” in the present invention means a layer composed of pixels and / or a black matrix used for a color filter.

  Furthermore, this invention provides the compound for bridge | crosslinking which has a structure represented by the said Formula (1). However, X in the formula represents a group having an oxiranyl group or a group having an oxetanyl group, and “*” represents a bond.

  Furthermore, this invention provides the compound for bridge | crosslinking represented by either of following formula (1-1)-(1-5).

(In the formulas (1-1) to (1-5), X ^{1 to} X ⁶ are each independently a hydrogen atom, a group having an oxiranyl group, a group having an oxetanyl group, or a group having a polymerizable unsaturated bond. Or an alkyl group having 1 to 6 carbon atoms, in which at least one of the groups is a group having an oxiranyl group, a group having an oxetanyl group, or a group having a polymerizable unsaturated bond, provided that the formula (1- In 1), two of X ^{1 to} X ⁶ are (meth) acryloyl groups, and the rest are methyl groups, and the (meth) acryloyl groups are bonded to two methyloxy groups on the same nitrogen atom. R ⁴ represents a hydrocarbon group having 1 to 12 carbon atoms, R ⁵ and R ⁶ each independently represent a hydrogen atom or —CH ₂ OX ¹ , and R ⁷ and R ⁸ represent each other Independently, an alkyl group having 1 to 6 carbon atoms is shown.)

The colored composition of the present invention has sufficient development resistance even at a low exposure amount, and can form a pixel and a black matrix having excellent solvent resistance.
Therefore, the colored composition of the present invention can be used very suitably for the production of color filters for various uses such as color filters for color liquid crystal display elements, color imaging tube elements, color sensors and the like in the electronic industry.

Hereinafter, the present invention will be described in detail.
Coloring composition will be described components of the colored composition of the present invention.

-(A) Colorant-
The colorant in the present invention is not particularly limited in color tone, and is appropriately selected according to the use of the obtained color filter, and may be any of a pigment, a dye, or a natural pigment. Since the color filter is required to have heat resistance, color developability and luminance, the colorant in the present invention is preferably an organic pigment, an inorganic pigment or an organic dye.
Examples of the organic pigment include compounds classified as pigments in the Color Index (CI; issued by The Society of Dyers and Colorists), specifically, the following Color Index (C.I. ) Names can be mentioned.

C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211;

C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;

C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 272;

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

  In the present invention, the organic pigment can be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof.

  On the other hand, examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and chromium oxide. Examples include green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

In addition, examples of the organic dye include compounds having the following color index (CI) names.
C. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Azo dyes such as Moldant Black 7;
C. 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. Anthraquinone dyes such as Disperse Blue 60;
C. I. Phthalocyanine dyes such as Pad Blue 5;
C. I. Basic Blue 3, C.I. I. Quinone imine dyes such as Basic Blue 9;
C. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Quinoline dyes such as Disperse Yellow 64;
C. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Nitro dyes such as Disperse Yellow 42.

If desired, organic pigments and inorganic pigments may be used after the particle surface is modified with a polymer. Examples of the polymer that modifies the particle surface of the pigment include the polymers described in JP-A-8-259876, various commercially available polymers or oligomers for dispersing pigments, and the like. As the polymer coating method on the carbon black surface, for example, methods disclosed in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969, and the like can be employed.
(A) A coloring agent can be used individually or in mixture of 2 or more types.

When the coloring composition of the present invention is used for forming a pixel, since the pixel is required to have high-definition color development and luminance, the colorant (A) is preferably a colorant having high color developability. Organic pigments and / or organic dyes are preferably used.
On the other hand, when the colored composition of the present invention is used for forming a black matrix, the black matrix is required to have a light-shielding property. Therefore, an organic pigment or carbon black is preferably used as the colorant (A).
In addition, the coloring composition of the present invention includes C.I. I. Pigment red 254, C.I. I. This is particularly useful in improving the solvent resistance of a colored layer formed using a colored composition containing at least one selected from the group consisting of CI Pigment Green 58 and carbon black. Moreover, the coloring composition of this invention is useful also at the point which improves the solvent resistance of the colored layer formed using the coloring composition containing an organic dye as (A) a coloring agent.

  In the colored composition of the present invention, the content of (A) the colorant is preferably 5% by mass or more, more preferably 10% by mass, based on the total solid content of the colored composition. The colored composition of the present invention has excellent solvent resistance even when the content of (A) the colorant is 30% by mass or more in the total solid content of the colored composition. In the present invention, the upper limit of the content of the colorant is preferably 70% by mass or less, particularly preferably 60% by mass or less, in the total solid content of the color composition, from the viewpoint of ensuring developability. Here, solid content is components other than the solvent mentioned later.

-(B) Binder resin-
The binder resin (B) in the present invention is not particularly limited, but is preferably an alkali-soluble resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as “carboxyl group-containing polymer”) is preferable, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “carboxyl group-containing unsaturated”). Monomer ") and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as" copolymerizable unsaturated monomers ") (copolymer having a carboxyl group) ) Is preferred. In the present specification, (meth) acrylic acid means methacrylic acid or acrylic acid.

Examples of the carboxyl group-containing unsaturated monomer include (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, and the like. it can. These carboxyl group-containing unsaturated monomers can be used alone or in admixture of two or more.
In the copolymer of the carboxyl group-containing unsaturated monomer and the copolymerizable unsaturated monomer, the copolymerization ratio of the carboxyl group-containing unsaturated monomer is preferably 5 to 50% by mass, more preferably 10%. -40 mass%. By copolymerizing the carboxyl group-containing unsaturated monomer in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

Examples of the copolymerizable unsaturated monomer include:
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;
Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (n = 2 -10) methyl ether (meth) acrylate, polypropylene glycol (n = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) ) Mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, Glyce Mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(meta ) Unsaturated carboxylic acid esters such as acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;
Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These copolymerizable unsaturated monomers can be used alone or in admixture of two or more.

  Specific examples of the copolymer having a carboxyl group include, for example, JP-A-7-140654, JP-A-10-31308, JP-A-10-300922, JP-A-11-174224, and JP-A-11. Examples thereof include copolymers disclosed in JP-A-258415, JP-A-2000-56118, JP-A-2004-101728, and the like.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

The polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the binder resin in the present invention is usually 1,000 to 45,000, preferably 3,000 to 30,000. If Mw is too small, the remaining film rate of the resulting film may be reduced, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, resolution may be reduced. In addition, the pattern shape may be damaged, and dry foreign matter may be easily generated during application by the slit nozzle method.
Further, the ratio (Mw / Mn) of the Mw of the binder resin in the present invention and the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) is Preferably it is 1.0-5.0, More preferably, it is 1.0-3.0.

  The binder resin in the present invention can be produced by a known method. In addition, the structure, Mw, and Mw / Mn can be controlled by the methods disclosed in JP2003-222717A, JP2006-259680A, and International Publication No. 07/029871.

In this invention, binder resin can be used individually or in mixture of 2 or more types.
In this invention, content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. If the content of the binder resin is too small, for example, the alkali developability may be decreased, or the storage stability of the resulting colored composition may be decreased. On the other hand, if the content is too large, the colorant concentration is relatively high. Therefore, it may be difficult to achieve the target color density when a thin film is formed.

-(C) Specific crosslinking agent (crosslinking compound)-
The (C) specific crosslinking agent in the present invention is a compound having a structure represented by the above formula (1), and is a component that polymerizes during the exposure or post-bake process to cure the coating film. By containing the (C) specific crosslinking agent, the colored composition of the present invention can form a colored layer having excellent development resistance and solvent resistance.

  In the above formula (1), the group having an oxiranyl group represented by X is not particularly limited, and examples thereof include a group represented by the following formula (X-1).

(In formula (X-1), R ^a represents a hydrogen atom or an alkyl group, R ^b represents an alkylene group, R ^c represents an ethylene group or a methylethylene group, and n represents 0 to 10.)

In the formula (X-1), as R ^a , a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is preferable, and a hydrogen atom or a methyl group is particularly preferable. R ^b is preferably an alkylene group having 1 to 6 carbon atoms such as a methylene group, ethylene group or methylethylene group, and n is preferably 0 to 5.

The group having an oxetanyl group represented by X is not particularly limited, and examples thereof include an alkyl oxetanyl group, a dialkyl oxetanyl group, an oxetanyl alkyl group, an alkyl oxetanyl alkyl group, and a dialkyl oxetanyl alkyl group. Here, the alkyl group substituted on the oxetanyl group preferably has 1 to 6 carbon atoms. Specific examples thereof include 3-C _1-6 alkyloxetane-3-yl-C _1-4 alkyl groups, and more specifically, 3-methyloxetane-3-ylmethyl group, 3-methyloxetane- A 3-ylethyl group, a 3-ethyloxetane-3-ylmethyl group, a 3-ethyloxetane-3-ylethyl group, and the like can be given.

  The group having a polymerizable unsaturated bond represented by X is not particularly limited. For example, an allyl group, a (meth) acryloyloxyalkyl group, a group represented by the following formula (X-2), Examples include a group represented by the following formula (X-3).

(In the formula (X-2), R ^d represents a hydrogen atom or a methyl group, R ^e independently represents an ethylene group or a methylethylene group, and l represents 2 to 10).

(In Formula (X-3), ^Rf represents a hydrogen atom or a methyl group, ^Rg represents an ethylene group or a methylethylene group, and m represents 0 to 10.)

  Specific examples of (meth) acryloyloxyalkyl groups include (meth) acryloyloxyethyl groups, (meth) acryloyloxypropyl groups, (meth) acryloyloxybutyl groups, and the like.

In the above formula (X-2), 1 is preferably 2 to 5. In the above formula (X-3), m is preferably 0 to 5. In the group -R ^g O- in the case where the group -R ^e O-, m is 2 or more, an oxyethylene group and an oxymethylethylene group may be mixed.

  (C) It is preferable that the structure of the specific crosslinking agent has two or more groups selected from a group having an oxiranyl group represented by X, a group having an oxetanyl group, and a group having a polymerizable unsaturated bond. X is preferably a group having an oxetanyl group, a group having a polymerizable unsaturated bond, or both of them.

  (C) As a specific crosslinking agent, what has a ureido structure, a glycoluril structure, a melamine structure, a benzoguanamine structure, or an imidazolidin-2-one structure is more preferable. Here, the melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and are a concept including a melamine compound, a benzoguanamine compound or a condensate thereof. Furthermore, (C) the specific crosslinking agent is a compound selected from the following formulas (1-1), (1-2), (1-3), (1-4) and (1-5). preferable.

(In the formula, X ^{1 to} X ⁶ each independently represent a hydrogen atom, a group having an oxiranyl group, a group having an oxetanyl group, a group having a polymerizable unsaturated bond, or an alkyl group having 1 to 6 carbon atoms. In the formulas, at least one of them is a group having an oxiranyl group, a group having an oxetanyl group, or a group having a polymerizable unsaturated bond, R ⁴ represents a hydrocarbon group having 1 to 12 carbon atoms, R ⁵ And R ⁶ each independently represent a hydrogen atom or —CH ₂ OX ¹ , and R ⁷ and R ⁸ each independently represent a C 1-6 alkyl group.

X ^{1 to} X ⁶ in the compounds of the above formulas (1-1) to (1-5) are groups having at least two groups having an oxiranyl group, a group having an oxetanyl group, or a polymerizable unsaturated bond. It is preferable.
The alkyl group having 1 to 6 carbon atoms in X ¹ ~X ^6, R ⁷ and R ^8, methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl Group, tert-butyl group, n-pentyl group, n-hexyl group and the like.

Examples of the hydrocarbon group having 1 to 12 carbon atoms in R ^4, an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 12 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a phenyl group.

Of the compounds of the above formulas (1-1) to (1-5), the compounds of the formulas (1-1) and (1-2) are more preferable from the viewpoint of development resistance and solvent resistance, and particularly the formula (1-1). ) Is preferred.
In formula (1-1), it is preferable that two or more of X ¹ to X ⁶ is a group having a group or a polymerizable unsaturated bond having an oxetanyl group, 2 of X ¹ to X ⁶ More preferably, five are groups having an oxetanyl group, or at least one of X ^{1 to} X ⁶ is a group having an oxetanyl group, and two or more are groups having a polymerizable unsaturated bond. .
In Formula (1-2), it is preferable that two or more of X ^{1 to} X ⁴ are a group having an oxetanyl group or a group having a polymerizable unsaturated bond, and R ⁴ is an aromatic having 6 to 12 carbon atoms. A group hydrocarbon group is preferred.
In the formula (1-3), it is preferable that X ¹ and ^{X 2} is a group having an oxetanyl group, ^{R 5} and ^{R 6} are -CH ₂ OX ^1, and X ¹ of the -CH ₂ OX ¹ is It is preferable that it is a C1-C6 alkyl group.

  (C) Specific examples of the specific crosslinking agent include compounds represented by the following (C-1) to (C-10).

In this invention, (C) specific crosslinking agent can be used individually or in mixture of 2 or more types.
In the present invention, the content of (C) the specific crosslinking agent is from 0.1 to 300 parts by mass, and further from 1 to 100 parts by mass of (B) binder resin, from the viewpoint of improving development resistance and improving solvent resistance. -200 mass parts is preferable.

-(D) Monomer having a polymerizable unsaturated bond-
In the present invention, by further using (D) a monomer having a polymerizable unsaturated bond (excluding the component (C) above), the curability of the formed colored layer can be further improved. it can. Examples of the monomer having a polymerizable unsaturated bond include a polyfunctional monomer having two or more polymerizable unsaturated bonds and a monofunctional monomer having one polymerizable unsaturated bond. be able to.

Examples of the polyfunctional monomer include:
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like, and their dicarboxylic acid-modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of both terminal hydroxylated polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactone;
Tris [2- (meth) acryloyloxyethyl] phosphate;
Isocyanuric acid ethylene oxide modified triacrylate;
Poly (meth) acrylate having a urethane structure;
Examples thereof include poly (meth) acrylate having a caprolactone structure.
These polyfunctional monomers can be used alone or in admixture of two or more.

Examples of the monofunctional monomer include divalent or higher polyvalent monomers such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl]. Mono [(meth) acryloyloxyalkyl] esters of monovalent carboxylic acids; mono (meth) acrylates of polymers having carboxy groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate; N-vinylsuccin Imido, N-vinylpyrrolidone, N-vinylphthalimide, N-vinyl-2-piperidone, N-vinyl-ε-caprolactam, N-vinylpyrrole, N-vinylpyrrolidine, N-vinylimidazole, N-vinylimidazolidine, N -Vinylindole, N-vinylindoline, N-vinylbenzimidazole, N-vinyl N-vinyl nitrogen-containing heterocyclic compounds such as rucarbazole, N-vinyl piperidine, N-vinyl piperazine, N-vinyl morpholine, N-vinyl phenoxazine; N- (meth) acryloyl morpholine and other commercially available products , M-5400, M-5600 (trade name, manufactured by Toagosei Co., Ltd.) and the like.
These monofunctional monomers can be used alone or in admixture of two or more.

  In the present invention, the monomer having a polymerizable unsaturated bond is preferably a polyfunctional monomer, and in particular, a poly (meth) acrylate of a trihydric or higher polyhydric alcohol or a dicarboxylic acid modified product thereof, urethane. A poly (meth) acrylate having a structure and a poly (meth) acrylate having a caprolactone structure are preferred. Examples of poly (meth) acrylates of trihydric or higher polyhydric alcohols or dicarboxylic acid modified products thereof include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate or monoesterified product of pentaerythritol triacrylate and succinic acid; pentaerythritol trimethacrylate and succinic acid Monoesterified product of dipentaerythritol Monoesterified product of taacrylate and succinic acid; monoesterified product of dipentaerythritol pentamethacrylate and succinic acid is preferable, and in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Monoesterified product of hexaacrylate or pentaerythritol triacrylate and succinic acid and monoesterified product of dipentaerythritol pentaacrylate and succinic acid have high strength of colored layer, excellent surface smoothness of colored layer, and unexposed This is preferable in that ground stains, film residues, and the like are hardly generated on the substrate and the light shielding layer.

  The content of the monomer having a polymerizable unsaturated bond in the present invention is preferably 5 to 400 parts by mass, more preferably 20 to 300 parts by mass with respect to 100 parts by mass of the (C) specific crosslinking agent. By containing a monomer having a polymerizable unsaturated bond at such a ratio, a colored composition having further excellent curability can be obtained.

-(E) Photopolymerization initiator-
Radiation sensitivity can be imparted to the colored composition by incorporating a photopolymerization initiator into the colored composition of the present invention. The term “radiation” as used herein means a substance including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.
In the present invention, (E) the photopolymerization initiator is used by (C) a specific cross-linking agent and (D) a polymerizable non-polymerizing agent by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates an active species capable of initiating polymerization of a monomer having a saturated bond.
As such a photopolymerization initiator, as a photo radical generator, for example, a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, an O-acyloxime compound, a benzoin compound, a benzophenone compound, Known compounds such as α-diketone compounds, polynuclear quinone compounds, and xanthone compounds can be exemplified.
Examples of the photoacid generator include known compounds such as an onium salt compound, a sulfone compound, a sulfonic acid ester compound, a quinonediazide compound, a sulfonimide compound, and a diazomethane compound. The triazine-based compounds exemplified as the photo radical generator are compounds that also function as a photo acid generator.

In this invention, a photoinitiator can be used individually or in mixture of 2 or more types, Of course, a photoradical generator and a photoacid generator can also be mixed and used.
In the present invention, the photoradical generator preferably contains at least one selected from the group of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

  Among preferred photoradical generators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

  Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′. -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, Examples thereof include 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

  When a biimidazole compound is used as the photoradical generator, it is preferable to use a hydrogen donor in terms of improving sensitivity. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, hydrogen donors can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

  In the present invention, when a photo radical generator other than a biimidazole compound such as an acetophenone compound is used, a sensitizer can be used in combination. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  In this invention, when using a photoradical generator, the content becomes like this. Preferably it is 1-2000 mass parts with respect to 100 mass parts of (C) specific crosslinking agents, More preferably, it is 5-1000 mass parts. If the content of the photoradical generator is too large, curing by exposure may be insufficient, while if too large, the formed colored layer tends to fall off the substrate during development.

  In the present invention, the photoacid generator preferably contains at least one selected from the group of onium salt compounds, sulfonimide compounds, and diazomethane compounds.

Among the preferred photoacid generators in the present invention, examples of the onium salt compound include diaryl iodonium salts, triarylsulfonium salts, triarylphosphonium salts and the like.
Specific examples of the diaryliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyl Iodonium-p-toluenesulfonate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroantimonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4 Methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (4- tert-butylphenyl) iodonium hexafluorophosphonate, bis (4-tert-butylphenyl) iodonium hexafluoroantimonate, bis (4-tert-butylphenyl) iodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium Trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4- ert- butyl phenyl) iodonium -p- toluenesulfonate, and the like.

  Specific examples of the triarylsulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphonate, Phenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroantimonate, 4-methoxy Phenyldiphenylsulfonium hexa Fluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroarsenate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenyl Thiophenyldiphenylsulfonium trifluoroace Over DOO,-p-4-phenylthiophenyl sulfonium can be given toluenesulfonate and the like.

  Specific examples of the triarylphosphonium salt include triphenylphosphonium tetrafluoroborate, triphenylphosphonium hexafluorophosphonate, triphenylphosphonium hexafluoroantimonate, triphenylphosphonium hexafluoroarsenate, triphenylphosphonium trifluoromethanesulfonate, Phenylphosphonium trifluoroacetate, triphenylphosphonium-p-toluenesulfonate, 4-methoxyphenyldiphenylphosphonium tetrafluoroborate, 4-methoxyphenyldiphenylphosphonium hexafluorophosphonate, 4-methoxyphenyldiphenylphosphonium hexafluoroantimonate, 4-methoxy Phenyldiphenylphosphonium hexa Fluoroarsenate, 4-methoxyphenyldiphenylphosphonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylphosphonium trifluoroacetate, 4-methoxyphenyldiphenylphosphonium-p-toluenesulfonate, tris (4-methoxyphenyl) phosphonium tetrafluoroborate , Tris (4-methoxyphenyl) phosphonium hexafluorophosphonate, tris (4-methoxyphenyl) phosphonium hexafluoroantimonate, tris (4-methoxyphenyl) phosphonium hexafluoroarsenate, tris (4-methoxyphenyl) phosphonium trifluoromethanesulfone Nato, tris (4-methoxyphenyl) phosphonium trifluoroacetate, tris (4-metho Shifeniru) phosphonium -p- toluenesulfonate, and the like.

  Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trimethyl). Fluoromethylsulfonyloxy) bicyclo- [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo- [2,2,1 ] -Hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo- [2,2,1] -heptane-5,6-oxy-2,3-dicarboximide N- (trifluoromethylsulfonyloxy) naphthalene-1,8-dicarboximide, N- Campanylsulfonyloxy) succinimide, N- (campanylsulfonyloxy) phthalimide, N- (campanylsulfonyloxy) diphenylmaleimide, N- (camphanylsulfonyloxy) bicyclo- [2,2,1] -hept-5 Ene-2,3-dicarboximide, N- (camphanylsulfonyloxy) -7-oxabicyclo- [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (camphor Nylsulfonyloxy) bicyclo- [2,2,1] -heptane-5,6-oxy-2,3-dicarboximide, N- (campanylsulfonyloxy) naphthalene-1,8-dicarboximide, N- (4-methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) Phthalimide, N- (4-methylphenylsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo- [2,2,1] -hept-5-ene-2,3-dicarboximide, N -(4-Methylphenylsulfonyloxy) -7-oxabicyclo- [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo- [ 2,2,1] -heptane-5,6-oxy-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) naphthalene-1,8-dicarboximide, N- (2-trifluoro) Methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-tri Fluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo- [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (2- Trifluoromethylphenylsulfonyloxy) -7-oxabicyclo- [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo- [ 2,2,1] -heptane-5,6-oxy-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) naphthalene-1,8-dicarboximide, and the like. .

  Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyl. Examples thereof include diazomethane, 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, and the like.

  In this invention, when using a photo-acid generator, the content is 0.1-100 mass parts normally with respect to 100 mass parts of (C) specific crosslinking agents, Preferably 0.3-50 mass parts It is. If the content of the photoacid generator is too small, curing by exposure may be insufficient. On the other hand, if the content is too large, foreign matter may be generated in the colored composition liquid or electrical characteristics may be deteriorated. is there.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of the additive include a thermal acid generator that promotes a curing reaction by opening a ring of an oxiranyl group, an oxetanyl group, and the like of the (C) specific crosslinking agent in the post-baking step.

  Specific examples of preferred thermal acid generators include 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4 -Hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluoroantimonate and the like.

  Other additives include, for example, fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); nonionic surfactants, cationic surfactants, anionic surfactants Surfactant such as an agent; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) ) -3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, 3-chloropropylmethyldi Adhesion promoters such as toxisilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), Antioxidants such as 2,6-di-t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; poly Sodium acrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1, 2-propanediol, 2-amino-1,3-propanediol, 4-amino- , It may be mentioned the residue improving agent such as 2-butane diol.

-Solvent-
Although the coloring composition of this invention contains the said (A)-(C) component and the other component added arbitrarily, normally, a solvent is mix | blended and it prepares as a liquid composition.
As the solvent, as long as the components (A) to (C) and other components constituting the colored composition are dispersed or dissolved and do not react with these components and have appropriate volatility, the solvent is appropriately used. You can choose to use.

As such a solvent, for example,
Alcohols such as methanol, ethanol, benzyl alcohol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, di Propylene glycol mono- - butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol (poly) alkylene glycol monoalkyl ethers such as monoethyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, N-butyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Ethyl 2-hydroxy-2-methylpropionate, 2 Hydroxy-3-methyl-butyric acid methyl, other esters such as ethyl 2-oxo-butyric acid;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide.

Among these solvents, benzyl alcohol, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol from the viewpoints of solubility, pigment dispersibility, coatability, etc. Mono-n-butyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, propylene glycol diacetate 1,3-butylene glycol diacetate, N-butyl acid, i-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methoxybutyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, 3-methoxypropion Ethyl acid, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Further, together with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid A high boiling point solvent such as diethyl, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate may be used in combination.
The high boiling point solvents can be used alone or in admixture of two or more.

  The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent from the colored composition is usually 5 from the viewpoint of applicability and stability of the obtained colored composition. An amount of ˜50 mass% is preferred, and an amount of 10˜40 mass% is particularly desirable.

  In the present invention, the coloring composition can be prepared by an appropriate method. For example, the coloring composition is prepared by mixing the components (A) to (C) together with a solvent and other components optionally added. Can do. As a preferable preparation method, for example, a bead mill, a roll mill, or the like is used together with a part of the component (B) in the presence of (A) a colorant in a solvent, a dispersant and, if necessary, a dispersion aid. Then, mix and disperse while pulverizing to obtain a pigment dispersion, which is prepared by adding (B) to (C) components and, if necessary, additional solvent and other components and mixing them. A method can be mentioned.

  As a dispersant used for the preparation of the pigment dispersion, for example, an appropriate dispersant such as a cationic, anionic, nonionic or amphoteric can be used, and a polymer dispersant is preferable. Specifically, a modified acrylic copolymer, an acrylic copolymer, polyurethane, polyester, a polymer copolymer alkylammonium salt or phosphate ester salt, a cationic comb graft polymer, and the like can be given. Here, the cationic comb graft polymer refers to a polymer having a structure in which two or more branched polymers are grafted to one molecule of a trunk polymer having a plurality of basic groups (cationic functional groups). Examples thereof include a polymer composed of a ring-opening polymer in which the trunk polymer part is polyethyleneimine and the branch polymer part is ε-caprolactone. Among these dispersants, modified acrylic copolymers, polyurethane, and cationic comb graft polymers are preferable.

  Such a dispersant is commercially available. For example, as a modified acrylic copolymer, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK Chemy (BYK Dispersbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (Lubrisol Co., Ltd.) Manufactured by Co., Ltd.), Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), Azisper PB821, Azisper PB822, Jisupa PB823, Adisper PB824, mention may be made of Ajisper PB827 (Ajinomoto Fine-Techno Co., Ltd.), and the like.

  These dispersants can be used alone or in admixture of two or more. The content of the dispersant is usually 100 parts by mass or less, preferably 0.5 to 100 parts by mass, more preferably 1 with respect to 100 parts by mass of the colorant (A) from the viewpoint of improving developability and the like. -70 mass parts, Especially preferably, it is 10-50 mass parts.

Color filter The color filter of the present invention comprises a colored layer formed from the colored composition of the present invention.
As a method for forming a color filter, first, a colored radiation-sensitive composition coating film is formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed, and a photo having a predetermined pattern is formed. There is known a method of obtaining pixels of each color by exposing radiation through a mask, developing to dissolve and remove unexposed portions, and then post-baking.
Specifically, first, if necessary, a light shielding layer (black matrix) is formed on the surface of the substrate so as to partition the pixel forming portion, and a red pigment, for example, is dispersed on the substrate. After applying a liquid composition of a colored composition imparted with radiation sensitivity, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Next, the coating film is exposed through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked to form a red pixel pattern. A pixel array arranged in an array is formed.
Thereafter, using the liquid composition of each coloring composition in which a green or blue pigment is dispersed, the liquid composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above, to thereby obtain a green pixel. By sequentially forming the array and the blue pixel array on the same substrate, a color filter in which the pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.
Further, the black matrix can be formed in the same manner as in the case of forming the pixel by using the colored composition of the present invention.

Examples of the substrate used when forming the pixel and / or the black matrix include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
When applying the liquid composition of the coloring composition to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet method is used. In particular, spin coating and slit die coating are preferable.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm as the film thickness after drying.

As the radiation used when forming the pixel and / or the black matrix, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, but the wavelength is in the range of 190 to 450 nm. Some radiation is preferred. Exposure of radiation is preferably 10~10,000J / m ^2. According to the colored composition of the present invention, 800 J / m ² or less of the exposure amount, and further it can form pixels excellent in solvent resistance at 600 J / m ² or less of the exposure amount.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

As a second method for forming a color filter, a method for obtaining pixels of each color by an ink jet method disclosed in Japanese Patent Laid-Open Nos. 4-2615033 and 7-318723 is also known.
The color filter of the present invention thus obtained is extremely useful for high-definition color liquid crystal surface elements, color image pickup tube elements, color sensors and the like.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
The color liquid crystal display element of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. Can be taken. Furthermore, a substrate on which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate on which an ITO (tin-doped indium oxide) electrode is formed are opposed to each other through a liquid crystal layer. The structure can be taken. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Preparation of pigment dispersion>
Preparation Example 1
(A) C.I. I. Pigment Red 254 (manufactured by Ciba Specialty Chemicals, trade name BK-CF), 15 parts by mass of BYK-LPN21324 as a dispersant (in terms of solid content), propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether as a solvent = A pigment dispersion (A-1) was prepared by treating the 80/20 (mass ratio) mixture with a bead mill using a solid concentration of 19% by mass.

Preparation Example 2
(A) 20 parts by mass of carbon black as a colorant, 4 parts by mass (in terms of solid content) of Disperbyk-167 as a dispersant, and 3-methoxybutyl acetate as a solvent so that the solid content concentration is 24% by mass, It processed by the bead mill and the pigment dispersion liquid (A-2) was prepared.

Preparation Example 3
(A) C.I. I. Pigment Green 58 (Dainippon Ink Chemical Co., Ltd.) / C.I. I. Pigment Yellow 150 = 60/40 (mass ratio) 15 parts by mass of a mixture, 4 parts by mass of BYK-LPN6919 as a dispersant (in terms of solid content), and propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether as a solvent = 90/10 (mass) Ratio) The mixture was used so that the solid content concentration was 19% by mass, treated with a bead mill, and mixed and dispersed for 12 hours with a bead mill to prepare a pigment dispersion (A-3).

Preparation Example 4
(A) C.I. I. Pigment green 36 / C.I. I. Pigment Yellow 150 = 60/40 (mass ratio) 15 parts by mass of the mixture, 4.0 parts by mass of BYK-LPN6919 as a dispersant (in terms of solid content), and propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether as the solvent = 90/10 (Mass ratio) The mixture was treated with a bead mill using a solid content concentration of 19% by mass, and mixed and dispersed for 12 hours with a bead mill to prepare a pigment dispersion (A-4).

Preparation Example 5
(A) C.I. I. 14.2 parts by mass of Pigment Green 58, 0.8 parts by mass of Solvent Yellow 33, an organic dye, 4.0 parts by mass of BYK-LPN6919 as a dispersant (in terms of solid content), and propylene glycol monomethyl ether acetate / Using a mixture of propylene glycol monomethyl ether = 90/10 (mass ratio) so as to have a solid content concentration of 19% by mass, the mixture was processed by a bead mill, mixed and dispersed for 12 hours by a bead mill, and a pigment dispersion (A- 5) was prepared.

<(B) Synthesis of binder resin>
Synthesis example 1
In a flask equipped with a condenser and a stirrer, 44.0 g of p-vinylbenzylglycidyl ether, 40.0 g of N-phenylmaleimide, and 16.0 g of benzyl methacrylate were dissolved in 300 g of propylene glycol monomethyl ether acetate, and 2,2′- Azobisisobutyronitrile (8.0 g) and α-methylstyrene dimer (8.0 g) were added, and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring and nitrogen bubbling and polymerized for 5 hours.
Subsequently, 17.0 g of methacrylic acid, 0.5 g of p-methoxyphenol and 4.4 g of tetrabutylammonium bromide were added to this reaction solution, and the mixture was reacted at a temperature of 120 ° C. for 9 hours. Further, 18.5 g of succinic anhydride was added and reacted at a temperature of 100 ° C. for 6 hours, then washed twice with the liquid temperature kept at 85 ° C., and concentrated under reduced pressure to obtain a binder resin [B- 1] was obtained. Mw of this binder resin [B-1] was 7,800.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 800 g of cyclohexanone, heated to 100 ° C. while injecting nitrogen gas into the flask, and at the same temperature, 60.0 g of styrene, 60.0 g of methacrylic acid, 65. methyl methacrylate. A mixture of 0 g, butyl methacrylate 65.0 g, and azobisisobutyronitrile 10.0 g was added dropwise over 1 hour, and further reacted at 100 ° C. for 3 hours, and then 2.0 g of azobisisobutyronitrile was added. What was dissolved in 50 g of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain a binder resin solution. After cooling to room temperature, about 2 g of binder resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added so that the nonvolatile content of the previously synthesized binder resin solution was 20% by mass. This was added to obtain a solution containing the binder resin [B-2]. Mw of this binder resin [B-2] was Mw = 30,000.

<(C) Synthesis of specific crosslinking agent>
Synthesis example 3
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a gas introduction tube, CYLE 300 (manufactured by Nippon Cytec Industries Co., Ltd., the main component is a compound represented by the following formula (a)), 580 g, 3-ethyl-3 -970 g of hydroxymethyloxetane (trade name OXT-101, manufactured by Toagosei Co., Ltd.), 580 g of toluene, and 2 g of p-toluenesulfonic acid were heated to 80 ° C. and reacted for 3 hours while distilling off the generated methanol. .
Thereafter, the mixture was neutralized with a 0.1N aqueous sodium hydroxide solution, and the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the non-volatile content was adjusted to 80% by mass. In this way, a solution containing a specific crosslinking agent in which all six methoxy groups in the compound represented by the following formula (a) were substituted with (3-ethyloxetane-3-yl) methoxy groups was obtained. Let the obtained specific crosslinking agent be specific crosslinking agent [C-1]. It should be noted that a compound in which all six methoxy groups in the compound represented by the following formula (a) are substituted with (3-ethyloxetane-3-yl) methoxy groups is obtained by ¹ H-NMR. And confirmed by GPC.

Synthesis example 4
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and gas introduction tube, 580 g of Cymel 300, 642 g of 3-ethyl-3-hydroxymethyloxetane, 580 g of propylene glycol monomethyl ether acetate, and 2 g of p-toluenesulfonic acid were added. The mixture was heated to 80 ° C. and reacted for 1 hour while distilling off the generated methanol.
Then, it neutralized with 0.1N sodium hydroxide aqueous solution, and the non volatile matter was 80 mass% by vacuum concentration. Thus, a specific crosslinking agent in which an average of about 4 of the 6 methoxy groups in the compound represented by the formula (a) is substituted with a (3-ethyloxetane-3-yl) methoxy group is used. A solution of a specific crosslinker mixture containing was obtained. Let the obtained specific crosslinking agent mixture be specific crosslinking agent [C-2]. In addition, a compound in which an average of about 4 of the 6 methoxy groups in the compound represented by the above formula (a) is substituted with a (3-ethyloxetane-3-yl) methoxy group is obtained. Was confirmed by ¹ H-NMR and GPC.

Synthesis example 5
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a gas introduction tube, 126 g of melamine, 202 g of 92% paraformaldehyde (Mitsubishi Gas Chemical Co., Ltd.), 1393 g of 2-hydroxyethyl acrylate, 520 g of 2-hydroxyethyl methacrylate Then, 256 g of methanol was charged, the temperature was raised to 80 ° C., and a methylolation reaction was performed at 80 ° C. for 1 hour, 1 g of p-toluenesulfonic acid was added, and an etherification reaction was performed at 80 ° C. for 3 hours.
Then, neutralize with 0.1N aqueous sodium hydroxide solution, distill off methanol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate by distillation under reduced pressure, replace the solvent with propylene glycol monomethyl ether acetate, 80%. Thus, among the six methoxy groups in the compound represented by the formula (a), an average of about 3 is substituted with an acryloyloxyethyloxy group and an average of about 1 is substituted with a methacryloyloxyethyloxy group. A solution of a specific cross-linking agent mixture containing the specific cross-linking agent was obtained. Let the obtained specific crosslinking agent mixture be specific crosslinking agent [C-3]. Of the six methoxy groups in the compound represented by the above formula (a), a compound having an average of about 3 substituted with an acryloyloxyethyloxy group and an average of about 1 with a methacryloyloxyethyloxy group It was confirmed by ¹ H-NMR and GPC that it was obtained.

Synthesis Example 6
A four-necked flask equipped with a stirrer, thermometer, reflux condenser and gas introduction tube was charged with 126 g of melamine, 202 g of 92% paraformaldehyde, 290 g of 3-ethyl-3-hydroxymethyloxetane, and 160 g of methanol, and the temperature was raised to 80 ° C. The methylolation reaction was carried out at 80 ° C. for 1 hour, 1 g of p-toluenesulfonic acid was added, and the etherification reaction was carried out at 80 ° C. for 3 hours.
Thereafter, the mixture was neutralized with a 0.1N aqueous sodium hydroxide solution, methanol and 3-ethyl-3-hydroxymethyloxetane were distilled off by distillation under reduced pressure, the solvent was replaced with propylene glycol monomethyl ether acetate, and the non-volatile content was 80 mass. %. Thus, a specific crosslinking agent in which an average of about 2 of the 6 methoxy groups in the compound represented by the formula (a) is substituted with a (3-ethyloxetane-3-yl) methoxy group is used. A solution of a specific crosslinker mixture containing was obtained. Let the obtained specific crosslinking agent mixture be specific crosslinking agent [C-4]. In addition, a compound in which about two of the six methoxy groups in the compound represented by the above formula (a) are substituted with (3-ethyloxetane-3-yl) methoxy group on average is obtained. Was confirmed by ¹ H-NMR and GPC.

Synthesis example 7
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a gas introduction tube, 580 g of Cymel 300, 325 g of 3-ethyl-3-hydroxymethyloxetane, 325 g of 2-hydroxyethyl acrylate, glycidol (manufactured by NOF Corporation) ) 104 g, toluene 580 g, and p-toluenesulfonic acid 1 g were charged and heated to 80 ° C., and the reaction was carried out for 3 hours while distilling off the generated methanol.
Thereafter, the mixture was neutralized with a 0.1N aqueous sodium hydroxide solution, and the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the non-volatile content was adjusted to 80% by mass. Thus, among the six methoxy groups in the compound represented by the formula (a), an average of about 2 is a (3-ethyloxetane-3-yl) methoxy group and an average of about 2 is acryloyl. A solution of a specific cross-linking agent mixture containing a specific cross-linking agent having an average of about 1 oxyethyloxy group substituted with a glycidyloxy group was obtained. Let the obtained specific crosslinking agent mixture be specific crosslinking agent [C-5]. Of the six methoxy groups in the compound represented by the formula (a), an average of about 2 is a (3-ethyloxetane-3-yl) methoxy group and an average of about 2 is acryloyloxyethyloxy. It was confirmed by ¹ H-NMR and GPC that a compound in which about 1 on average was substituted with a glycidyloxy group was obtained.

Synthesis example 8
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and gas introduction tube, melamine 126 g, 92% paraformaldehyde 202 g, 2-hydroxyethyl acrylate 1393 g, 2-hydroxyethyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) 280 g Then, 256 g of methanol was added, the temperature was raised to 80 ° C., and a methylolation reaction was performed at 80 ° C. for 1 hour, 1 g of paratoluenesulfonic acid was added, and an etherification reaction was performed at 80 ° C. for 3 hours.
Then, neutralize with 0.1N sodium hydroxide aqueous solution, distill off methanol, 2-hydroxyethyl acrylate, 2-hydroxyethyl vinyl ether by distillation under reduced pressure, replace the solvent with propylene glycol monomethyl ether acetate, 80% by mass. Thus, among the six methoxy groups in the compound represented by the formula (a), an average of about 3 is substituted with an acryloyloxyethyloxy group and an average of about 1 is substituted with a vinyloxyethyloxy group. A solution of a specific cross-linking agent mixture containing the specific cross-linking agent was obtained. Let the obtained specific crosslinking agent mixture be specific crosslinking agent [C-6]. Of the six methoxy groups in the compound represented by the above formula (a), a compound having an average of about 3 substituted with an acryloyloxyethyloxy group and an average of about 1 with a vinyloxyethyloxy group It was confirmed by ¹ H-NMR and GPC that it was obtained.

Synthesis Example 9
To a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a gas introduction tube, 351 g of UFR65 (mainly a compound represented by the following formula (b)) manufactured by Nippon Cytec Industries, Ltd., 3-ethyl-3- Hydroxymethyloxetane (313 g), toluene (350 g), and p-toluenesulfonic acid (2 g) were charged, heated to 80 ° C., and reacted for 3 hours while distilling off the generated methanol.
Thereafter, the mixture was neutralized with a 0.1N aqueous sodium hydroxide solution, and the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the non-volatile content was adjusted to 80% by mass. In this way, a specific crosslinking agent in which an average of about 2 out of 4 methoxy groups in the compound represented by the following formula (b) is substituted with (3-ethyloxetane-3-yl) methoxy group A solution of a specific crosslinker mixture containing was obtained. Let the obtained specific crosslinking agent mixture be specific crosslinking agent [C-7]. In addition, a compound in which about 2 of the 4 methoxy groups in the compound represented by the following formula (b) are substituted with (3-ethyloxetane-3-yl) methoxy group is obtained. Was confirmed by ¹ H-NMR and GPC.

Synthesis Example 10
To a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a gas inlet tube, 575 g of Cymel 1123 (mainly a compound represented by the following formula (c)) manufactured by Nippon Cytec Industries, Ltd., 3-ethyl- 302 g of 3-hydroxymethyloxetane, 575 g of toluene, and 2 g of p-toluenesulfonic acid were charged and heated to 80 ° C., and the reaction was carried out for 3 hours while distilling off the generated methanol and ethanol.
Thereafter, the mixture was neutralized with a 0.1N aqueous sodium hydroxide solution, and the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the non-volatile content was adjusted to 80% by mass. In this way, a specific crosslinking agent in which an average of about 2 of the 4 alkoxy groups in the compound represented by the following formula (c) is substituted with a (3-ethyloxetane-3-yl) methoxy group A solution of a specific crosslinker mixture containing was obtained. Let the obtained specific crosslinking agent mixture be specific crosslinking agent [C-8]. In addition, a compound in which an average of about 2 of the 4 alkoxy groups in the compound represented by the following formula (c) is substituted with a (3-ethyloxetane-3-yl) methoxy group is obtained. Was confirmed by ¹ H-NMR and GPC.

(In the formula, R is a methyl group or an ethyl group.)

Synthesis Example 11
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and gas introduction tube, 126 g of melamine, 202 g of 92% paraformaldehyde, 464 g of 2-hydroxyethyl acrylate, 116 g of 3-ethyl-3-hydroxymethyloxetane, and 32 g of methanol The temperature was raised to 80 ° C. and methylolation reaction was carried out at 80 ° C. for 1 hour, 1 g of p-toluenesulfonic acid was added, and etherification reaction was carried out at 80 ° C. for 3 hours.
Then, neutralize with 0.1N aqueous sodium hydroxide solution, distill off methanol, 2-hydroxyethyl acrylate, 3-ethyl-3-hydroxymethyloxetane by distillation under reduced pressure, and replace the solvent with propylene glycol monomethyl ether acetate. The nonvolatile content was 80%. Thus, among the six methoxy groups in the compound represented by the formula (a), an average of about 4 is an acryloyloxyethyloxy group and an average of about 1 is (3-ethyloxetane-3- I) A solution of a specific cross-linking agent mixture containing a specific cross-linking agent substituted with a methoxy group was obtained. Let the obtained specific crosslinking agent mixture be specific crosslinking agent [C-9]. Of the six methoxy groups in the compound represented by the formula (a), an average of about 4 is an acryloyloxyethyloxy group and an average of about 1 is (3-ethyloxetane-3-yl) methoxy. It was confirmed by ¹ H-NMR that a compound substituted with a group was obtained.

<Preparation and evaluation of coloring composition>
Example 1
Preparation of coloring composition (A) 100.0 parts by mass of pigment dispersion (A-1) as a colorant, (B) 26.0 parts by mass of a binder resin [B-1] solution as a binder resin and a binder resin [B- 2) 6.6 parts by mass of the solution, (C) 9.9 parts by mass of the solution containing the specific crosslinking agent [C-1] as the specific crosslinking agent, and (D) Toagosei as a monomer having a polymerizable unsaturated bond 5.4 parts by mass of M-402 (dipentaerythritol hexaacrylate) manufactured by Toyo Gosei Co., Ltd. and TO-1382 (monoesterified product of dipentaerythritol pentaacrylate and succinic acid, dipentaerythritol hexaacrylate and dipenta Erythritol pentaacrylate mixture) 3.6 parts by mass, (E) Irga manufactured by Ciba Specialty Chemicals as photopolymerization initiator 907 (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one) 4.3 parts by mass, ethyl 3-ethoxypropionate as a solvent, solid content of the colored composition A colored radiation-sensitive composition was prepared by mixing to a concentration of 20% by mass.
The obtained colored radiation-sensitive composition was evaluated according to the following procedure. The evaluation results are shown in Table 1.

Pattern formation The colored radiation-sensitive composition obtained was applied to a soda glass substrate with a SiO ₂ film formed on the surface to prevent elution of sodium ions, using a spin coater, and then on a hot plate at 90 ° C. Was pre-baked for 2 minutes to form a film having a thickness of 1.7 μm.
Next, after cooling the substrate to room temperature, each wavelength of 365 nm, 405 nm, and 436 nm was applied to the coating film through a photomask having a plurality of slits having different sizes within a width of 5 to 50 μm using a high-pressure mercury lamp. Exposed ultraviolet light was exposed. The exposure amount at this time was 500 J / m ² . Thereafter, the substrate was subjected to shower development using a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, then washed with ultrapure water and air-dried. Thereafter, post-baking was performed in a clean oven at 220 ° C. for 30 minutes to form a pixel array in which red stripe pixel patterns were arranged on the substrate.

Evaluation of residue The substrate obtained in the formation of the pattern was observed, and whether or not the residue remained in the unexposed portion was evaluated in the following three stages.
A: A residue is not recognized.
B: A little residue is recognized.
C: Many residues are observed.

Evaluation of development resistance In the formation of the above pattern, when the film thickness ratio before and after the development of the pixel pattern having a width of 50 μm (film thickness after development × 100 / film thickness before development) is 95% or more, “A”, The case where the film thickness ratio before and after the development was less than 95%, or a part of the pattern was found to be chipped was evaluated as “B”, and the case where the pattern was completely peeled off from the substrate was evaluated as “C”.
Further, the minimum value of the width of the pixel pattern that remained without peeling off the entire pattern was evaluated as the minimum pattern width (μm) that can be formed.

Solvent resistance evaluation The obtained colored radiation-sensitive composition was applied to a soda glass substrate having a SiO ₂ film formed on its surface to prevent elution of sodium ions, using a spin coater, and then a hot plate at 90 ° C. The film was pre-baked for 2 minutes to form a film having a thickness of 1.7 μm.
Next, after cooling the substrate to room temperature, the coating film was exposed to ultraviolet rays including wavelengths of 365 nm, 405 nm, and 436 nm without using a photomask using a high-pressure mercury lamp. The exposure amount at this time was 500 J / m ² . Thereafter, the substrate was subjected to shower development using a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, then washed with ultrapure water and air-dried. Thereafter, post-baking was performed in a clean oven at 220 ° C. for 30 minutes to form a red cured film on the substrate.
Next, the substrate on which the red cured film was formed was immersed in N-methylpyrrolidone at 60 ° C. for 30 minutes. As a result, the film thickness ratio before and after immersion (film thickness after immersion × 100 / film thickness before immersion) was 95% or more and N-methylpyrrolidone after immersion was not colored at all. The case where the film thickness ratio before and after immersion was less than 95% or the N-methylpyrrolidone after immersion was slightly colored was evaluated as “B”, and the case where cracks occurred after immersion was evaluated as “C”.

Examples 2 to 10 and Comparative Examples 1 to 3
In Example 1, as shown in Table 1, a colored radiation-sensitive composition was prepared in the same manner as in Example 1 except that the type and content (parts by mass) of each component were changed.
Subsequently, various evaluation was performed like Example 1 using the obtained colored radiation-sensitive composition. The results are shown in Table 1.

In Table 1, each component is as follows.
c-1: Cymel 300 manufactured by Nippon Cytec Industries, Ltd. (compound of formula (a) as a main component)
c-2: Nippon Cytec Industries, Ltd. Cymel 1123 (compound of formula (c) as a main component)
D-1: Dipentaerythritol hexaacrylate (trade name M-402, manufactured by Toagosei Co., Ltd.)
D-2: monoesterified product of dipentaerythritol pentaacrylate and succinic acid, dipentaerythritol hexaacrylate and mixture of dipentaerythritol pentaacrylate (trade name TO-1382, manufactured by Toagosei Co., Ltd.)
D-3: Pentaerythritol tetraacrylate (trade name M-450, manufactured by Toagosei Co., Ltd.) E-1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (product) Name Irgacure 907, manufactured by Ciba Specialty Chemicals)
E-2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name IRGACURE OX02, Ciba Specialty・ Made by Chemicals
EEP: ethyl 3-ethoxypropionate MBA: 3-methoxybutyl acetate

  As is clear from Table 1, when the coloring composition of the present invention containing (A) a colorant, (B) a binder resin, and (C) a specific cross-linking agent is used, even if the exposure amount is low, the pixel pattern It can be seen that fine pixels having no chipping and excellent solvent resistance can be formed.

Claims (9)

A coloring composition comprising (A) a colorant, (B) a binder resin, and (C) a compound having a structure represented by the following formula (1).

(Wherein, X represents a group having a group or oxetanyl group having oxiranyl groups, "*" indicates a bond.)   The coloring composition according to claim 1, wherein the component (C) has a ureido structure, a glycoluril structure, a melamine structure, a benzoguanamine structure or an imidazolidin-2-one structure. The component (C) is a compound selected from the following formulas (1-1), (1-2), (1-3), (1-4) and (1-5). Coloring composition.

(In the formula, X ^{1 to} X ⁶ each independently represent a hydrogen atom, a group having an oxiranyl group, a group having an oxetanyl group, a group having a polymerizable unsaturated bond, or an alkyl group having 1 to 6 carbon atoms. at least one thereof in each formula, .R ⁴ is a group having a group or oxetanyl group having oxiranyl groups is a hydrocarbon group having 1 to 12 carbon atoms, R ⁵ and R ⁶ independently of one another, A hydrogen atom or —CH ₂ OX ¹ , and R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 6 carbon atoms.   The coloring composition according to any one of claims 1 to 3, further comprising (D) a monomer having a polymerizable unsaturated bond (excluding the component (C)).   Furthermore, (E) The coloring composition of any one of Claims 1-4 containing a photoinitiator.   The color filter provided with the colored layer formed using the coloring composition of any one of Claims 1-5.   A color liquid crystal display device comprising the color filter according to claim 6. A crosslinking compound having a structure represented by the following formula (1).

(Wherein, X represents a group having a O Kisetaniru group, "*" indicates a bond.) A crosslinking compound represented by any one of the following formulas (1-1) to (1-5).

(In the formula, X ^{1 to} X ⁶ each independently represent a hydrogen atom, a group having an oxiranyl group, a group having an oxetanyl group, a group having a polymerizable unsaturated bond, or an alkyl group having 1 to 6 carbon atoms. , at least one of which in each formula, .R ⁴ is a group having a O Kisetaniru group represents a hydrocarbon group having 1 to 12 carbon atoms, R ⁵ and R ⁶ independently of one another, a hydrogen atom or -CH ₂ OX ¹ , R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 6 carbon atoms.