TWI595316B - Coloring composition, color filter and display element - Google Patents

Description

Coloring composition, color filter, and display element

The present invention relates to a coloring composition, a color filter, and a display element, and more particularly to a coloring composition for a transmissive or reflective type color liquid crystal display element, a solid-state imaging element, an organic EL display element, and A coloring layer useful for a color filter used for electronic paper or the like; a color filter having a coloring layer formed using the coloring composition; and a display element including the color filter.

When a color filter is produced using a coloring sensitizing radiation composition, it is known that a colored radiation-sensitive composition is applied onto a substrate and dried, and then the dried coating film is irradiated with radiation to have a desired pattern shape (hereinafter referred to as "exposure"). A method of obtaining each color pixel by development (Patent Documents 1 to 2). Moreover, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is also known (Patent Document 3). In addition, a method of obtaining each color pixel by an inkjet method using a colored thermosetting resin composition (Patent Document 4) is also known.

In recent years, with the high color purity of a color liquid crystal display element, the concentration of the colorant contained in the coloring composition tends to gradually increase. Further, in the coloring composition for forming a color filter for an organic EL display element, the concentration of the coloring agent contained in the coloring composition must be very large in order to reproduce the desired color tone due to the relationship between the white light spectrum emitted from the organic EL element. Gao is a fact. Therefore, the problem of occurrence of residue and stain on the substrate on the unexposed portion during development becomes more and more remarkable. On the other hand, in Patent Documents 5 to 8, in order to suppress the occurrence of development residue, it is proposed to use a polymerizable compound having an alkylene group as a curing component.

Leading patent literature Patent literature

Patent Document 1 JP-A-2-144502

Patent Document 2 Japanese Patent Publication No. 3-53201

Patent Document 3, JP-A-6-35188

Patent Document 4, JP-A-2000-310706

Patent Document 5, JP-A-2008-107773

Patent Document 6 JP-A-2009-109921

Patent Document 7 JP-A-2009-244748

Patent Document 8 JP-A-2009-244807

The polymerizable compound having an alkylene group is useful in the sense of suppressing development residue, but a colored liquid crystal display is formed by shower-developing a colored layer such as a pixel on a glass substrate having a low radiation reflectance. When a color filter for an element or a color filter for an organic EL display element is used, there is a problem that the pixel pattern defect and the pixel pattern linearity are deteriorated. Further, in the manufacture of a color filter for a solid-state imaging device disclosed in Patent Documents 5 to 8, a painting is formed by liquid-repellent (paddle development) on a wafer having a high exposure radiation reflectance. The pattern is not easy to occur.

Therefore, the subject of the present invention is to provide a coloring composition which can suppress the occurrence of defects such as development residue and pixels in development during development, and suppress deterioration of linearity of a colored pattern. Further, an object of the present invention is to provide a color filter including a coloring layer formed using the colored composition, and a display element including the color filter.

As a result of active investigation by the present inventors, it has been found that the above problems can be solved by using a specific polymerizable compound in combination.

In other words, the present invention provides a colored composition comprising (A) a colorant, (B) a binder resin, and (C) a polymerizable compound; characterized by containing the following (C1) compound and (C2) compound as (C) (C1) A compound having three or more polymerizable unsaturated groups and at least one of three or more polymerizable unsaturated groups is a group represented by the following formula (1) (hereinafter also referred to as "polymerization" (C2) (C2) A compound having two or more polymerizable unsaturated groups and at least one of two or more polymerizable unsaturated groups is a group represented by the following formula (2) (hereinafter) Also known as "polymeric compound (C2)").

In the formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an exoethyl or propanediyl group, m represents an integer of 1 to 12, and "*" represents a linkage. 〕

In the formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkanediyl group having 1 to 10 carbon atoms, n represents an integer of 1 to 5, and "*" represents a linkage. . 〕

Moreover, the present invention provides a color filter comprising a coloring layer formed using the colored composition, and a display element including the color filter. Here, the "colored layer" means each color pixel, black matrix, black spacer, and the like used in the color filter.

When the color filter is produced by using the colored composition of the present invention, not only the development residue and the coloring pattern such as a pixel during development can be suppressed, but also the linearity of the colored pattern can be suppressed.

Therefore, the coloring composition of the present invention is extremely suitable for use in color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. The production of various color filters led by the light sheet.

Hereinafter, the present invention will be described in detail.

[Coloring composition]

The constituent components of the colored composition of the present invention will be described below.

- (A) colorant -

In the present invention, the coloring agent (A) is not particularly limited as long as it has coloring properties. However, the color filter is preferably selected from at least one selected from the group consisting of pigments and dyes because of high color purity, brightness, contrast, and the like.

The pigment may be any of an organic pigment and an inorganic pigment, and a specific example of the organic pigment, and a color index (CI) name may be cited as CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, CI. Pigment Red 254, CI Pigment Red 264, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Blue 15:6, CI Pigment Blue 80, CI Pigment Yellow 83, CI Pigment Yellow 129, CI Pigment Yellow 138 , CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 211, CI Pigment Orange 38, CI Pigment Violet 23, and the like. Specific examples of the inorganic pigment include carbon black and titanium black.

The pigment is also preferably a lake pigment, and specifically, a triarylmethane dye or a dibenzopyran dye is used as a seed of an isopoly acid or a heteropoly acid. The triarylmethane-based lake pigments are disclosed in, for example, JP-A-2011-186043, and the like, and the dibenzopipelane-based lake pigments are disclosed, for example, in JP-A-2010-191304.

Further, the dye is preferably a dibenzopyran-based dye, a triarylmethane-based dye, a cyanine dye, an onion-based dye, or an azo-based dye. More specifically, Japanese Laid-Open Patent Publication No. 2010-32999, JP-A-2010-254964, JP-A-2011-138094, International Publication No. 10/123071, and JP-A-2011-116803 An organic dye described in, for example, JP-A-2011-174987, JP-A-2011-174987, and the like.

The pigments and dyes of the present invention may be used alone or in combination of two or more.

When a pigment is used as the coloring agent in the present invention, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof, as needed. Further, the pigment may be used as a resin to modify the surface of the particle as needed. The resin of the surface of the modified pigment particle is, for example, a developer resin described in JP-A-2001-108817 or a commercially available resin for pigment dispersion. Further, the pigment can be used by refining the primary particles by a so-called salt milling method. For the method of the salt milling method, for example, the method disclosed in JP-A 08-179111 can be employed.

(A) The content ratio of the coloring agent is usually from 5 to 70% by mass in the total solid content of the coloring composition from the viewpoint of forming a black matrix having high luminance, excellent color purity, or a light-shielding property. 5 to 60% by mass. Here, the "solid component" is a component other than the solvent described later.

When the colorant content ratio is increased, the residue tends to be generated during development, and the coloring pattern defect and the coloring pattern linearity tend to be deteriorated. However, if the coloring composition of the present invention is used, even if the coloring agent content ratio is all solid content The high concentration of 30% by mass or more can also suppress the occurrence of defects in the development residue and the coloring pattern and the deterioration of the linearity of the coloring pattern.

In particular, in the coloring composition containing a green coloring agent for forming a green pixel, the exposure radiation transmittance in the ultraviolet field is essentially The tendency to increase the colorant content ratio is low, and it is difficult to achieve both the development residue and the color pattern linearity. The colored composition of the present invention is particularly suitable for use in such green compositions.

When a pigment is used as a coloring agent in the present invention, it may be used in combination with a dispersing agent and a dispersing aid as needed. As the dispersing agent, a suitable dispersing agent such as a cationic system, an anionic system or a nonionic system can be used, and a polymer dispersant is preferred. Specific examples thereof include an urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkylphenyl ether dispersant, and a polyethylene glycol diester. A dispersing agent, a sorbitan fatty acid ester dispersing agent, a polyester dispersing agent, an acrylic dispersing agent, etc.

Such dispersing agents are commercially available, and acrylic dispersing agents such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK), and urethane dispersion can be exemplified. Agents such as Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2164 (above BYK), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), polyethyleneimine The dispersing agent is, for example, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), a polyester-based dispersing agent such as AJISPER PB821, AJISPER PB822, AJISPER PB880, and AJISPER PB881 (manufactured by Ajinomoto Fine-Techno Co., Ltd.). Further, the dispersant content can be appropriately determined within the range not impairing the object of the present invention.

The dispersing aid may, for example, be a pigment derivative, and specific examples thereof include copper indigo, pyrrolopyrroledione, and quinoline yellow sulfonic acid derivatives. Further, the content of the dispersing aid can be appropriately determined within the range not impairing the object of the present invention.

- (B) Adhesive Resin -

The binder resin in the coloring composition of the present invention is not particularly limited, and is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. In particular, it is preferably a polymer having a carboxyl group (hereinafter referred to as a "carboxyl group-containing polymer"), and examples thereof include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (b1)") and others. A copolymer of a copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (b2)").

The unsaturated monomer (b1) may, for example, be (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2-(methyl)acryloxyethyl), ω- Carboxypolycaprolactone mono(meth)acrylate and p-vinylbenzoic acid.

These unsaturated monomers (b1) can be used individually or in mixture of 2 or more types.

Further, the unsaturated monomer (b2) may, for example, be an N-position substituted maleimide such as N-phenylmaleimide or N-cyclohexylmethyleneimine; benzene An aromatic vinyl compound such as ethylene, α -methylstyrene, p-hydroxystyrene, p-hydroxy- α -methylstyrene, p-vinylbenzyl epoxidized propyl ether, and acenaphthylene; methyl (Meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate Ester, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate , polyethylene glycol (degree of polymerization 2~10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isodecyl ( Methyl) acrylate, tricyclo [5.2.1.0 ^2,6 ]decane-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-Hydroxyphenyl (meth) acrylate, ethylene oxide modification of p-isopropylphenol (A Acrylate, epoxy propyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(methyl) propylene methoxymethyl] oxocyclobutane (oxetane) and (meth) acrylate such as 3-[(meth)acryloxymethyl]-3-ethyloxycyclobutane; cyclohexyl vinyl ether, isodecyl vinyl ether, tricyclo [5.2 .1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether and vinyl ether such as 3-(vinyloxymethyl)-3-ethyloxycyclobutane; polystyrene, poly A macromolecular monomer having a mono(meth)acryl fluorenyl group at the terminal of a polymer molecular chain such as a methyl (meth) acrylate, a poly-n-butyl (meth) acrylate or a polydecane.

These unsaturated monomers (b2) can be used individually or in mixture of 2 or more types.

In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. %. By copolymerizing the unsaturated monomer (b1) in this range, a coloring composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), for example, JP-A-7-140654, JP-A-8-259876, JP-A-10-31308, and JP-A Copolymerization disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Fit.

In the present invention, the adhesive resin can be used, for example, in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylonitrile group in a branched chain, as disclosed in Japanese Laid-Open Patent Publication No. 2008-181095.

Further, in the present invention, as the binder resin, for example, a copolymer comprising an epoxy group-containing (meth) acrylate-containing unsaturated monomer such as epoxy propyl (meth) acrylate may be used. A hydroxyl group produced by the reaction of the unsaturated monomer (b1), and a copolymer which further reacts the polybasic acid anhydride.

Examples of the polybasic acid anhydride include maleic anhydride, fumaric anhydride, methyl maleic anhydride, methyl fumaric anhydride, methylene succinic anhydride, tetrahydrophthalic anhydride, and methyl group. a dibasic anhydride such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hemic anhydride, phthalic anhydride, and naphthalene-2,3-dicarboxylic anhydride; a polybasic acid anhydride of a tribasic acid or the like such as cyclohexane-1,2,4-tricarboxylic anhydride or trimellitic anhydride; cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride , norbornane tetracarboxylic dianhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, diphenyl ketone tetracarboxylic acid An acid anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, or a polybasic acid dianhydride having a tetrabasic acid or the like such as hydrazine-3,4,9,10-tetracarboxylic dianhydride.

In the present invention, the weight average molecular weight (Mw) of the binder resin measured by GPC (dissolving solvent: tetrahydrofuran) is usually from 1,000 to 100,000, preferably from 3,000 to 50,000. According to these aspects, it is easy to form a film having a good residual film ratio, a pattern shape, heat resistance, electrical characteristics, and resolution, and it is also possible to suppress the occurrence of dry foreign matter when applied by a slit nozzle method.

Further, the ratio (Mw/Mn) of the weight average molecular weight of the binder resin to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC (dissolving solvent: tetrahydrofuran) in the present invention is preferably 1.0 to 5.0, preferably 1.0~3.0.

In the present invention, the binder resin can be produced by a conventional method, and can be controlled by a method disclosed in, for example, JP-A-2003-222717, JP-A-2006-259680, and International Publication No. 07/029871. Construction, Mw and Mw/Mn.

In the present invention, the binder resin may be used singly or in combination of two or more.

The content of the binder resin in the present invention is preferably 10 to 1000 parts by mass, particularly preferably 20 to 500, based on 100 parts by mass of the (A) colorant. Quantities. According to these aspects, the alkali developability and the storage stability and the chromaticity characteristics of the colored composition can be improved.

- (C) Polymeric Compound -

In the present invention, the (C) polymerizable compound is characterized in that the polymerizable compound (C1) and the polymerizable compound (C2) are used in combination. The desired effect can be obtained by using a polymerizable compound (C1) having a highly hydrophilic polymerizable functional group and a polymerizable compound (C2) having a low hydrophilic polymerizable functional group.

First, the polymerizable compound (C1) will be described.

The polymerizable compound (C1) has three or more polymerizable unsaturated groups, and at least one of the three or more polymerizable unsaturated groups is a group represented by the following formula (1), and is not particularly limited as long as it is such a compound. Further, when the polymerizable compound (C1) has two or more groups represented by the following formula (1), R ¹ , R ² and m of each group may be the same or different.

In the formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an ethylidene group or a propylene group, m represents an integer of 1 to 12, and "*" represents a linkage. 〕

In the formula (1), examples of the propylenediyl group of R ² include propane-1,1-diyl, propane-1,2-diyl and propane-1,3-diyl, and among them, propane-1 is preferable. , 2-diyl.

R ^{2 is} preferably an exoethyl group from the viewpoints of suppressing development of a developing residue such as development residue, a pixel, and the like, and deterioration of the linearity of the coloring pattern.

The polymerizable compound (C1) is preferably a compound represented by the following formula (1-1) to (1-3) from the viewpoints of suppressing the development of the coloring pattern such as the development residue and the pixel, and the deterioration of the linearity of the coloring pattern. .

[In the formula (1-1), one or more of the three X ¹ groups are groups represented by the formula (1), and the rest are (meth) acryloxy groups, and the symbols in the formula (1) are synonymous with the above. 〕

[In the formula (1-2), one or more of the four X ² are groups represented by the formula (1), and the rest are (meth) acryloxy group or hydroxyl group, and the symbols in the formula (1) are as described above. Synonymous. Only when the number of the groups represented by the formula (1) is a ¹ and the number of (meth)acryloxy groups is b ¹ , a ¹ + b ¹ ≧ 3 . 〕

[In the formula (1-3), one or more of the six X ³ groups are the groups represented by the formula (1), and the rest are (meth) acryloxy groups or hydroxyl groups, and the symbols in the formula (1) are as described above. Synonymous. Only when the number of the groups represented by the formula (1) is a ² and the number of (meth)acryloxy groups is b ² , a ² + b ² ≧ 3 . 〕

The base represented by the formula (1) in the formula (1-1) should be adjusted so that the total of m is preferably an integer of 1 to 36, preferably an integer of 2 to 30, and preferably an integer of 2 to 20. More preferably, it is an integer from 3 to 10.

The base represented by the formula (1) in the formula (1-2) should be adjusted so that the total of m is preferably an integer of 1 to 48, preferably an integer of 2 to 40, and preferably an integer of 2 to 16. More preferably, it is an integer from 4 to 8.

The base represented by the formula (1) in the formula (1-3) should be adjusted so that the total of m is preferably an integer of 1 to 72, more preferably an integer of 3 to 60, and preferably an integer of 3 to 24. More preferably, it is an integer from 6 to 12.

The polymerizable compound represented by the formula (1-1) is A-GLY-3E sold by Shin-Nakamura Chemical Co., Ltd. (in the formula (1-1), each m is 3 in total, and R ¹ is hydrogen. Atom, R ² is a compound of an ethyl group), A-GLY-6E (in the formula (1-1), each m is a total of 6, R ¹ is a hydrogen atom, and R ² is a compound of an ethyl group), A -GLY-9E (in the formula (1-1), each m is 9 in total, R ¹ is a hydrogen atom, R ² is a compound which stretches an ethyl group), and A-GLY-20E (in the formula (1-1) Each of m is a total of 20, R ¹ is a hydrogen atom, R ² is a compound of an ethyl group, and the like.

The polymerizable compound represented by the formula (1-2) and the polymerizable compound represented by the formula (1-3) include KAYARAD RP-1040 sold by Nippon Kayaku Co., Ltd. (the formula (1-2) Wherein a ¹ + b ¹ = 4, each m is 4 in total, R ¹ is a hydrogen atom, R ² is a compound of a pendant ethylene group, and KAYARAD DPEA-12 (in the formula (1-3), a ² + b ² = 6, each m is 12 in total, R ¹ is a hydrogen atom, R ² is a compound of a pendant ethyl group, and the like.

In the present invention, the polymerizable compound (C1) may be used singly or in combination of two or more.

Next, the polymerizable compound (C2) will be described.

The polymerizable compound (C2) has two or more polymerizable unsaturated groups, and at least one of the two or more polymerizable unsaturated groups is a group represented by the following formula (2), and is not particularly limited as long as it is such a compound. Further, when the polymerizable compound (C2) has two or more groups represented by the following formula (2), R ³ , R ⁴ and n of each group may be the same or different.

In the formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl 2 group having 1 to 10 carbon atoms, n represents an integer of 1 to 5, and "*" represents a linkage. 〕

In the formula (2), R ⁴ represents an alkanediyl group having 1 to 10 carbon atoms, preferably an alkanediyl group having 4 to 8 carbon atoms, more preferably a linear alkanediyl group having 4 to 6 carbon atoms or a carbon number. a branched alkanediyl group of 6-8. Specific examples thereof include a methylene group, an ethyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. , 2-methylpentane-1,5-diyl, 4,4-dimethylhexane-2,6-diyl and 2,4-dimethylhexane-2,6-diyl and the like.

Further, in the formula (2), n represents an integer of 1 to 5, and is preferably 1 or 2 from the viewpoint of improving the curability of the colored composition. Further, when n is 2 or more, the plural R ⁴ may be the same or different, and is preferably the same.

The polymerizable compound (C2) is preferably a compound having four or more groups represented by the formula (2) from the viewpoint of improving the desired effect, and particularly preferably having 4 to 6 groups represented by the formula (2). Compound.

Examples of the polymerizable compound (C2) include various components such as trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentenol, glycerin, and trimethylol melamine. A polyfunctional (meth) acrylate obtained by reacting an alcohol with (meth)acrylic acid and a lactone. The lactones may, for example, be α-lactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, heptanolactone, 4-methylcaprolactone, 3 , 5,5-trimethylcaprolactone and 3,3,5-trimethylcaprolactone and the like. In the present invention, the polymerizable compound (C2) represented by the following formula (2-1) is suitable from the viewpoint of improving the desired effect.

[In the formula (2-1), one or more of the six R's are a group represented by the formula (2), and the rest are a group represented by the following formula (3) or a hydrogen atom, and the respective symbols in the formula (2) are as described above. Synonymous. 〕

[In the formula (3), R ⁵ represents a hydrogen atom or a methyl group, and "*" represents a linkage. 〕

In the formula (2-1), n is preferably an integer of from 1 to 3, more preferably 1 or 2. Further, each n is preferably an integer of 2 to 20, more preferably an integer of 2 to 15, and particularly preferably an integer of 2 to 12.

When 1 to 5 of the 6 Rs are the bases of the formula (2), and the rest are the bases of the formula (3), 2 to 5 of the 6 Rs are preferably represented by the formula (2). The base is the group represented by the formula (3), and particularly preferably 4 to 5 are the groups represented by the formula (2), and the rest are the groups represented by the formula (3).

The polymerizable compound (C2) represented by the formula (2-1) includes KAYARAD DPCA series and DPCA-20 sold by Nippon Kayaku Co., Ltd. (in the formula (2-1), 2 of 6 R One is a group represented by the formula (2), and four are groups represented by the formula (3), n is 1, R ³ and R ⁵ are each a hydrogen atom, and R ⁴ is a pentane-1,5-diyl group. The compound is a main component), DPCA-30 (in the formula (2-1), three of the six Rs are a group represented by the formula (2), and three of the groups represented by the formula (3), n is 1, R ³ and R ⁵ are each a hydrogen atom, R ⁴ is a pentane-1,5-diyl group-based compound, and DPCA-60 (in the formula (2-1), 6 R's are For the group represented by the formula (2), n is 1, R ^{3 is} a hydrogen atom, R ⁴ is a pentane-1,5-diyl group-based compound, and DPCA-120 (in the formula (2-) 1), 6 R are all groups represented by the formula (2), n is 2, R ^{3 is} a hydrogen atom, R ⁴ is a pentane-1,5-diyl group-based compound, and the like.

In the present invention, the polymerizable compound (C2) may be used singly or in combination of two or more kinds.

In the present invention, the polymerizable compound (C1) and the polymerizable compound (C2) are preferably the same as (C3) a polyfunctional (meth) group having no group represented by the formula (1) and a group represented by the formula (2). Acrylate (hereinafter also referred to as "polymerizable compound (C3)") can be used in combination to further enhance the desired effect. The polymerizable compound (C3) may, for example, be a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, a polyfunctional (meth) acrylate having a hydroxyl group, and a polyfunctional isocyanate. B carbamate A polyfunctional (meth) acrylate having a carboxyl group obtained by reacting an ester (meth) acrylate and a (meth) acrylate having a hydroxyl group with an acid anhydride.

Among the polymerizable compounds (C3), a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound having a valence of 3 or more with (meth)acrylic acid is preferable, and trimethylolpropane tris(III) is particularly preferable. Acrylate, neopentyl alcohol tri(meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

In the present invention, the polymerizable compound (C3) may be used singly or in combination of two or more.

In the (C) polymerizable compound of the present invention, a compound having two or more epoxy groups, a compound having two or more N-alkoxymethylamino groups, or the like can be further used, whereby the thermosetting property of the colored composition can be improved.

In the present invention, the content of the (C) polymerizable compound is preferably from 10 to 1,000 parts by mass, particularly preferably from 20 to 500 parts by mass, per 100 parts by mass of the (B) binder resin. According to these aspects, the hardenability and the alkali developability are improved, and the occurrence of stains, residual film, and the like on the unexposed portion of the substrate or on the light shielding layer can be suppressed.

The content of the polymerizable compound (C1) in the present invention is preferably 1 part by mass or more, more preferably 10 parts by mass or more, particularly preferably 20 parts by mass or more, based on 100 parts by mass of the (B) binder resin. It is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, and particularly preferably 70 parts by mass or less. The content of the polymerizable compound (C1) is preferably from 1 to 150 parts by mass, more preferably from 10 to 100 parts by mass, particularly preferably from 20 to 70 parts by mass, per 100 parts by mass of the (B) binder resin.

In addition, the content of the polymerizable compound (C2) is preferably 1 part by mass or more, more preferably 10 parts by mass or more, particularly preferably 25 parts by mass or more, and preferably 99% by mass based on 100 parts by mass of the (B) binder resin. The amount is preferably 80 parts by mass or less, and particularly preferably 70 parts by mass or less. The content of the polymerizable compound (C2) is preferably from 1 to 99 parts by mass, more preferably from 10 to 80 parts by mass, particularly preferably from 25 to 70 parts by mass, per 100 parts by mass of the (B) binder resin.

The content ratio (mass ratio) of the polymerizable compound (C1) to the polymerizable compound (C2) is preferably from 90:10 to 10:90, more preferably from 75:25 to 25:75, particularly preferably from 60:40 to 30: 70.

In the present invention, when the polymerizable compound (C3) is used, the content thereof is preferably from 1 to 99 parts by mass, particularly preferably from 5 to 50 parts by mass, per 100 parts by mass of the (B) binder resin. With these aspects, the desired effect can be further enhanced.

-(D) Photopolymerization initiator -

The coloring composition of the present invention may contain (D) a photopolymerization initiator. Thereby, the coloring composition can be imparted with radiation. The (D) photopolymerization initiator used in the present invention is a compound which emits an active species which causes polymerization of the (C) polymerizable compound by radiation exposure such as visible light, ultraviolet light, far ultraviolet ray, electron beam and X-ray. .

Such photopolymerization initiators may, for example, be 9-oxosulfur (thioxanthone) compound, acetophenone compound, diimidazole compound, three Compound, O-mercapto oxime compound, sulfonium salt compound, benzoin compound, diphenyl ketone compound, α-diketone compound, polynuclear oxime compound, diazo compound, sulfhydrazine sulfonate A compound, a phosphonium salt compound, or the like.

In the present invention, the photopolymerization initiator may be used singly or in combination of two or more. The photopolymerization initiator is preferably selected from the group consisting of 9-oxosulfur Compound, acetophenone compound, diimidazole compound, three At least one of the group of the compound and the O-mercapto lanthanide compound.

9-oxygen sulfide in a photopolymerization initiator suitable for the present invention Specific examples of the compound can be exemplified by 9-oxosulfur 2-chloro 9-oxosulfur 2-methyl 9-oxosulfur 2-isopropyl 9-oxosulfur 4-isopropyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 2,4-dimethyl 9-oxosulfur 2,4-diethyl 9-oxosulfur And 2,4-diisopropyl 9-oxosulfur Wait.

Further, specific examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)butan-1-one and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Polinylphenyl)butan-1-one and the like.

Further, specific examples of the diimidazole-based compound include 2.2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole and 2.2'-bis (2). ,4-dichlorobenzene)-4,4',5,5'-tetraphenyl-1,2'-diimidazole and 2.2'-bis(2,4,6-trichlorobenzene)-4,4' , 5,5'-tetraphenyl-1,2'-diimidazole, and the like.

Further, when a diimidazole-based compound is used as a photopolymerization initiator, it is preferred to use a hydrogen donor in combination from the viewpoint of improving sensitivity. Here, the "hydrogen donor" is a compound which can supply a hydrogen atom by exposing a radical generated from a diimidazole-based compound. Examples of the hydrogen donor include a thiol-based hydrogen donor such as 2-hydrothiobenzothiazole or 2-hydrothiobenzoxazole, 4,4'-bis(dimethylamino)diphenyl ketone, and 4,4. An amine-based hydrogen donor such as '-bis(diethylamino)diphenyl ketone. In the present invention, the hydrogen donor may be used alone or in combination of two or more. In view of the fact that it is possible to further improve the sensitivity, it is preferred to use one or more kinds of thiol-based hydrogen donors and one or more amine-based hydrogen donors.

Again, the three Specific examples of the compound can be exemplified by 2,4,6-tris(trichloromethyl)-s-three. 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-three And 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three Three of the halogenated methyl groups a compound.

Further, specific examples of the O-mercapto fluorene-based compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoguanidinopurine), and B. Ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), ethyl ketone, 1- [9-Ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), ethyl ketone ,1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazole In addition to -3-yl]-, 1-(O-ethyl fluorenyl), an oxime ester compound described in International Publication No. 08/078678, and JP-A-2011-132215.

When a photopolymerization initiator other than a diimidazole-based compound such as an acetophenone-based compound is used in the present invention, a sensitizer may be used in combination. Such sensitizers may, for example, be 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, 4-diethylaminophenyl benzene. Ketone, 4-dimethylaminopropiophenone, 4-dimethylamino benzoic acid ethyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-two Ethylamino-3-(4-diethylaminobenzimidyl)coumarin and 4-(diethylamino)chalcone and the like.

The content of the photopolymerization initiator in the present invention is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, per 100 parts by mass of the (C) polymerizable compound. By these aspects, the hardenability and film properties can be improved.

-(E) solvent -

The colored composition of the present invention contains the components (A) to (C) and any other components added thereto, and is usually prepared by mixing a solvent to prepare a liquid composition.

When the solvent is dispersed or dissolved to form the components (A) to (C) of the colored composition and does not react with the components, and has moderate volatility, it can be suitably used.

Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and Ethylene 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, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl (poly)alkane monoalkyl ethers such as ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; alkyl lactate such as methyl lactate and ethyl lactate; a (cyclo)alkyl alcohol such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol or cyclohexanol; a ketone such as diacetone alcohol Alcohols; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc. Alcohol monoalkyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and other ethers such as tetrahydrofuran; methyl ethyl ketone, ring Ketones such as ketone, 2-heptanone and 3-heptanone; diacetate such as propylene glycol diacetate, 1,3-butanediol diacetate and 1,6-hexanediol diacetate; Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate and 3-methyl- Alkoxycarboxylates such as 3-methoxypropionic acid butyl ester; ethyl acetate, n-propyl acetate Ester, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, Other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate and ethyl 2-oxybutyrate; toluene and An aromatic hydrocarbon such as toluene; a decylamine such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone; or an indoleamine.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate are preferable from the viewpoints of solubility, pigment dispersibility, and coating properties. Ester, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3- Heptone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 - ethyl ethoxypropionate, butyl 3-methyl-3-methoxypropionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, Ethyl butyrate, isopropyl butyrate, n-butyl butyrate and ethyl pyruvate.

In the present invention, the solvent may be used singly or in combination of two or more.

The solvent content is not particularly limited, but the total concentration of each component of the coloring composition excluding the solvent is preferably from 5 to 50% by mass, particularly preferably from 10%, from the viewpoints of coating properties and stability of the coloring composition obtained. 40% by mass.

-additive-

The colored composition of the present invention may also contain various additives as needed.

Examples of the additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); surfactants such as fluorine-based surfactants and lanthanoid surfactants; and ethylene trimethoxy group. Decane, ethylene triethoxy decane, ethylene tris(2-methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2 -aminoethyl)-3-aminopropylmethyltrimethoxydecane, 3-aminopropyltriethoxy Decane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Baseline, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, and 3-hydrothiopropyltrimethoxy An adhesion promoter such as quinone; an antioxidant such as 2,2-thiobis(4-methyl-6-t-butanol) and 2,6-di-t-butanol; 2-(3-t- Ultraviolet absorbers such as butyl-5-methyl-2-hydroxybenzene)-5-chlorobenzotriazole and alkoxydiphenyl ketone; anti-agglomerating agents such as sodium polyacrylate; malonic acid, adipic acid , methylene succinic acid, methyl maleic acid, fumaric acid, methyl fumaric acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino group Residue improver such as 1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol and 4-amino-1,2-butanediol; succinic acid-[ Developing property such as 2-(meth)acryloxyethyl ester, phthalic acid mono [2-(methyl) propylene methoxyethyl] ester, and ω-carboxy polycaprolactone (meth) acrylate Improvement agent; special publication 2008-242078, etc. A fluorene oligomer having a reactive functional group or the like is disclosed.

The colored composition of the present invention can be prepared by a suitable method, and the preparation method can be prepared, for example, by mixing (A) to (C) components with (E) a solvent or any other component added arbitrarily. When the pigment is used as the (A) colorant, the pigment is pulverized in the presence of a dispersant in the solvent (E), optionally with one part of the component (B), using, for example, bead milling or roll milling. Further, the mixture is mixed and dispersed to form a pigment dispersion liquid, and then a component (B) to (C) component and a solvent or other component which is further added as needed are added to the pigment dispersion liquid, and the mixture is prepared by mixing.

[Color filter and method of manufacturing the same]

The color filter of the present invention is provided with a coloring layer formed using the colored composition of the present invention.

The method for producing a color filter is the first method. First, a light shielding layer (black matrix) is formed on the surface of the substrate as needed to distinguish the portions forming the pixels. Next, a liquid composition of the radiation sensitive coloring composition of the present invention containing, for example, a green coloring agent is applied onto the substrate, and then pre-baked to evaporate the solvent to form a coating film. Next, after the coating film was exposed to the reticle, it was developed with an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, by post-baking, a pixel matrix in which the green pixel patterns are arranged in a predetermined arrangement is formed.

Next, using a red or blue radiation-sensitive coloring composition, the coating, pre-baking, exposure, development, and post-baking of the respective radiation-sensitive coloring compositions are performed in the same manner as described above, and red pixels are sequentially formed on the same substrate. The matrix of the three primary color pixels of the matrix and the blue pixel matrix. Thereby, a color filter in which three primary color pixel matrices of red, green, and blue are arranged on the substrate is obtained. However, the order of formation of the respective color pixels in the present invention is not limited to the above. Further, in the first method of producing a color filter, any one of the blue, green, and red pixel matrix may be used to form a coloring layer using the coloring composition of the present invention.

Further, the black matrix can be formed by photolithography forming a desired pattern by sputtering or vapor deposition of a metal film such as chromium, or by using a radiation-containing coloring composition containing a black colorant, and the aforementioned painting. The formation of the elements in the same manner. The colored composition of the present invention is also suitable for the formation of the black matrix.

Examples of the substrate used in forming the color filter include glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, and polyimine. When glass is used as the substrate, the reflectance of the exposure radiation is low, and in particular, the hardening reaction of the edge portion of the pixel or the black matrix is insufficient, and the coloring pattern defect and the linearity of the coloring pattern are likely to be deteriorated. These problems will not easily occur if the radiation sensitive coloring composition of the present invention is used.

Further, on the substrates, appropriate pretreatment such as drug treatment, plasma treatment, ion plating, sputtering, gas phase reaction, and vacuum vapor deposition using a decane coupling agent or the like may be performed as needed.

When the radiation-sensitive coloring composition is applied to a substrate, a suitable coating method such as a spray method, a roll coating method, a spin coating method, a slit nozzle coating method, or a bar coating method may be employed, and a spin coating method is particularly preferable. Slit nozzle coating method.

The pre-baking is usually carried out by combining drying under reduced pressure with heating and drying. Drying under reduced pressure usually reaches 50 to 200 Pa. Further, the heating and drying conditions are usually about 1 to 10 minutes at 70 to 110 °C.

The coating thickness is usually from 0.6 to 8 μm, preferably from 1.2 to 5 μm, in terms of film thickness after drying.

The radiation source used when forming the pixel and/or the black matrix may be, for example, 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, or the like, or an argon ion mine. Laser sources such as laser, YAG laser, XeCl excimer laser and nitrogen electric radiation. Ultraviolet LEDs can also be used for the exposure source. It is preferably radiation with a wavelength in the range of 190 to 450 nm.

The amount of radiation exposure is generally 10 to 10000 J/m ² .

Further, the alkaline developing solution is preferably, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-dioxinbicyclo-[5.4.0]-7-undecene. And an aqueous solution of 1,5-dioxabicyclo-[4.3.0]-5-decene.

A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline developer in an appropriate amount. Further, after alkaline development, water washing is usually carried out.

The development processing method can be applied to a shower development method, a spray development method, a dipping development method, a liquid-covering development method, or the like. The developing condition is preferably 5 to 300 seconds at normal temperature. When the shower development method is used, if the development pressure is increased or the development time is prolonged, development residue is less likely to occur, and the edges of the pixels or the black matrix tend to be easily degraded. Moreover, the linearity of the colored patterns is extremely sensitive to development conditions. In particular, when the concentration of the colorant contained in the colored composition is increased, it is difficult to find development conditions in which no development residue, no pixel pattern defect, and linearity of the pixel pattern are deteriorated. When the radiation-sensitive coloring composition of the present invention is used, such problems are less likely to occur when the shower developing method is employed.

The post-baking conditions are usually about 10 to 60 minutes at 120 to 280 °C. The thickness of the pixel film thus formed is usually 0.5 to 5 μm, preferably 1 to 3 μm.

Moreover, the second method of producing a color filter is a method of obtaining each color pixel by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei 7-318723, No. 2000-310706. In this method, a partition wall having a shading function is first formed on the surface of the substrate. Next, in the partition wall formed, for example, the hot hardening of the present invention containing a green coloring agent The liquid composition of the chemically colored composition is ejected by an inkjet device, and then pre-baked to evaporate the solvent. Next, after the coating film is exposed as needed, a green pixel pattern is formed by post-baking hardening.

Next, a red pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above, using each of the thermosetting coloring compositions of red or blue. Thereby, a color filter in which three primary color pixel patterns of red, green, and blue are arranged on the substrate is obtained. However, the order of formation of the respective color pixels in the present invention is not limited to the above. Further, in the second method of producing a color filter, any one of the blue, green, and red pixel matrix may be used to form the coloring layer using the coloring composition of the present invention.

Further, the partition wall not only has a light-shielding function, but also exhibits a function of not mixing the coloring compositions of the respective colors ejected in the region, and therefore has a thicker film thickness than the black matrix used in the first method. Therefore, the partition wall is usually formed using a black sensitizing radioactive composition.

The substrate or the radiation source used in forming the color filter, and the manner and conditions of pre-baking or post-baking are the same as the first method described above. The thickness of the pixel film formed by the ink jet method is as high as the height of the partition wall.

On the pixel pattern thus obtained, a transparent conductive film is formed by sputtering after forming a protective film as needed. After the transparent conductive film is formed, a spacer may be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, and may be a spacer having a light-shielding property (black spacer). The colored composition of the present invention is also suitable for forming the black spacer.

The color filter of the present invention thus obtained is extremely useful for color liquid crystal display elements, color photographic tube elements, color sensors, organic EL display elements, and electronic paper. The coloring composition of the present invention is particularly suitable for producing a color filter for a color liquid crystal display element or a color filter for an organic EL display element in which a colored layer is formed by a shower development method on a glass substrate.

[display component]

The display element of the present invention is provided with the color filter of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

The color liquid crystal display element having the color filter of the present invention can be suitably constructed. For example, a color filter is formed on another substrate other than the substrate for driving the thin film transistor (TFT), and the substrate for driving and the substrate on which the color filter is formed are transmitted through the liquid crystal layer. Further, on the surface of the substrate for driving the thin film transistor (TFT), the substrate on which the color filter is formed and the substrate on which the ITO (tin-doped indium oxide) electrode is formed are transmitted through the liquid crystal layer. The latter structure can greatly increase the aperture ratio and has the advantage of obtaining a bright high-definition liquid crystal display element.

The liquid crystal display element including the color filter of the present invention may include a backlight element using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). The white LED can be, for example, a combination of a red LED and a green LED and a blue LED to obtain a white light white LED, a blue LED and a red LED, and a green color. Color phosphor combination color mixing to obtain white light white LED, blue LED and red light emitting phosphor and green light emitting phosphor combined color to obtain white light white LED, blue LED and YAG fluorescent body mixed color to obtain white light The white LED, the blue LED and the orange illuminating phosphor and the green illuminating phosphor are combined to obtain a white light white LED, and the ultraviolet LED and the red illuminating phosphor, the green illuminating phosphor and the blue illuminating phosphor are combined. The white color of the white light is obtained by mixing colors.

For a liquid crystal display element having the color filter of the present invention, a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, an IPS (In-Planes Switching) type, a VA (Vertical Alignment) type, and an OCB can be applied. Suitable liquid crystal mode (Optically Compensated Birefringence) type.

Further, the organic EL display device having the color filter of the present invention can be suitably configured, and the structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242 can be used.

Further, the electronic paper including the color filter of the present invention may have a suitable structure, and the structure disclosed in Japanese Laid-Open Patent Publication No. 2007-41169, for example.

[Examples]

Hereinafter, embodiments of the present invention will be further specifically described by way of examples. However, the invention is not limited to the following examples.

<Synthesis of Adhesive Resin> Synthesis Example 1

In a flask equipped with a condenser and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was charged and replaced with nitrogen. Heat to 80 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, and 2-hydroxyethyl methacrylate 15 at the same temperature. Parts by mass, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenyl maleimide, 15 parts by mass of succinic acid mono(2-propenyl oxiranyl), and 2, A mixed solution of 2'-azobis(2,4-dimethylvaleronitrile) 6 parts by mass was dropped over 1 hour, and the temperature was maintained at this temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour to obtain a binder resin (B-1) solution (solid content concentration: about 33% by mass). The obtained binder resin (B-1) had a Mw of 12,200 and an Mn of 6,500.

Synthesis Example 2

In a flask equipped with a condenser and a stirrer, 144 parts by mass of cyclohexanone was charged and replaced with nitrogen. Heating to 80 ° C, 48 parts by mass of cyclohexanone, 28.8 parts by mass of methacrylic acid, 18 parts by mass of butyl methacrylate, 18 parts by mass of methyl methacrylate, 2-ethylhexyl EO-modified acrylic acid at the same temperature 18 parts by mass of ester (manufactured by Toagosei Co., Ltd., trade name M-120), a mixed solution of 18 parts by mass of cyclohexyl methacrylate and 37.2 parts by mass of glyceryl methacrylate, and 48 parts by mass of cyclohexanone and 2 A mixed solution of 8.4 parts by mass of 2'-azobis(2,4-dimethylvaleronitrile) was dropped every 2 hours, and the temperature was maintained at this temperature for 1 hour. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and further polymerization was carried out for 1 hour. Next, 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., trade name Karenz MOI) was 34.3 parts by mass (95 mol% relative to the glycerol methacrylate molar number) and 4-A Oxyphenol 0.36 The mixed solution was added dropwise under air bubble conditions for 15 minutes, and the addition reaction was carried out for 1.5 hours. Thereafter, the solution was cooled to room temperature, and cyclohexane ketone was added to adjust the solid content concentration to 36% by mass to obtain a binder resin (B-2) solution. The obtained binder resin (B-2) had Mw = 12,800, Mn = 6000, and an iodine value of 36.0 g / 100 g.

Synthesis Example 3

In a flask equipped with a condenser and a stirrer, 132 parts by mass of propylene glycol monomethyl ether acetate was charged and replaced with nitrogen. Heating to 90 ° C, 28 parts by mass of propylene glycol monomethyl ether acetate, tricyclo [5.2.1.0 ^2,6 ]decane-8-yl acrylate (Hitachi Chemical Co., Ltd., trade name FA-513AS) 40 mass a mixed solution of 60 parts by mass of epoxy methacrylate, and 7 parts by mass of 2,2'-azobisvaleronitrile and 40 parts by mass of propylene glycol monomethyl ether acetate in 2 hours each The mixture was dropped and maintained at this temperature for 1 hour. Thereafter, the reaction solution was heated to 100 ° C and further polymerized for 1 hour. Next, 36 parts by mass of methacrylic acid, 2 parts by mass of tetrabutylammonium bromide, 0.35 parts by mass of 4-methoxyphenol, and 10 parts by mass of propylene glycol monomethyl ether acetate were added, and the addition reaction was carried out at 110 ° C for 5 hours. . Further, 48 parts by mass of tetrahydrophthalic anhydride (Nippon Chemical Industry Co., Ltd., trade name RIKACID TH) was charged, and an addition reaction was carried out at 100 ° C for 4 hours. The solution was cooled to room temperature, and propylene glycol monomethyl ether acetate was added thereto to adjust the solid content concentration to 33% by mass to obtain a binder resin (B-3) solution. The obtained binder resin (B-3) had Mw = 12,000 and Mn = 6,600.

<Preparation of Pigment Dispersion> Modulation example 1

(A) Colorant: 4 parts by mass of CI Pigment Red 254, 15 parts by mass of CI Pigment Red 177, and 1 part by mass of CI Pigment Yellow 150, and Disperbyk-2001 (made by BYK Corporation, solid content concentration: 45.0% by mass) A mixed liquid of 11 parts by mass of the solution and 69 parts by mass of propylene glycol methyl ether acetate as a solvent, and mixed/dispersed by bead milling for 12 hours to prepare a pigment dispersion liquid (A-1).

Modulation example 2

(A) The coloring agent used was 10 parts by mass of CI Pigment Green 58 and 10 parts by mass of CI Pigment Yellow 150, and 11 parts by mass of a solution of Disperbyk-2001 (solid content concentration: 45.0% by mass by BYK Co., Ltd.) was used as a dispersing agent, and a solvent was used. A mixed liquid of 69 parts by mass of propylene glycol methyl ether acetate was mixed/dispersed by bead milling for 12 hours to prepare a pigment dispersion liquid (A-2).

Modulation example 3

(A) The coloring agent used was 15 parts by mass of CI Pigment Green 58 and 5 parts by mass of CI Pigment Yellow 138, and 12.5 parts by mass of a solution of BYK-LPN-21116 (solid content concentration: 40.0% by mass by BYK Co., Ltd.) was used as a dispersing agent, and The solvent mixture was mixed with 67.5 parts by mass of propylene glycol methyl ether acetate, and mixed/dispersed by bead milling for 12 hours to prepare a pigment dispersion liquid (A-3).

Modulation example 4

(A) The colorant is 15 parts by mass of C.I. Pigment Green 7 and 5 parts by mass of C.I. Pigment Yellow 150, and the dispersant is used. 11 parts by mass of a solution of Disperbyk-2001 (manufactured by BYK Co., Ltd., solid content: 45.0% by mass), and a solvent mixture of 69 parts by mass of propylene glycol methyl ether acetate, which were mixed/dispersed by bead milling for 12 hours to prepare pigment dispersion. Liquid (A-4).

Modulation example 5

(A) The coloring agent used was 18 parts by mass of CI Pigment Blue 15:6 and 2 parts by mass of CI Pigment Violet, and 12.5 parts by mass of a solution of BYK-LPN-21116 (manufactured by BYK Co., Ltd., solid content concentration: 40.0% by mass) was used. A mixed liquid of 67.5 parts by mass of propylene glycol methyl ether acetate was used as a solvent, and the pigment dispersion liquid (A-5) was prepared by bead mill mixing/dispersion for 12 hours.

Modulation example 6

(A) The coloring agent used was 12 parts by mass of CI Pigment Green 7 and 8 parts by mass of CI Pigment Yellow 129, and 12.5 parts by mass of a solution of BYK-LPN-21116 (solid content concentration: 40.0% by mass by BYK Co., Ltd.) was used as a dispersing agent, and The solvent mixture was mixed with 67.5 parts by mass of propylene glycol methyl ether acetate, and mixed/dispersed by bead milling for 12 hours to prepare a pigment dispersion liquid (A-6).

Modulation example 7

(A) Colorant: 12 parts by mass of CI Pigment Green 58 and 5 parts by mass of CI Pigment Green 7 and 3 parts by mass of CI Pigment Yellow 185, and BYK-LPN-21116 (by BYK, solid content concentration 40.0) A mixture of 12.5 parts by mass of the solution and a solvent of 67.5 parts by mass of propylene glycol methyl ether acetate was mixed and dispersed by bead milling for 12 hours to prepare a pigment dispersion liquid (A-7).

<Modulation and evaluation of coloring composition> Example 1

100 parts by mass of the pigment dispersion liquid (A-1), 70 parts by mass of the binder resin solution (B-1) of (B) binder resin, and ethylene oxide oligomerization as the polymerizable compound (C1) 10 parts by mass of modified neopentyltetraol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPEA-12), ε -caprolactone-modified dipentaerythritol as polymerizable compound (C2) 6 parts by mass of hexaacrylate (manufactured by Nippon Kagaku Co., Ltd., trade name KAYARAD DPCA-60), 2-benzyl-2-dimethylamino-1-(4-) as photoinitiator of (D) 11 parts by mass of morphylphenyl)butanone-1 (manufactured by BASF Corporation, trade name IRGACURE 369), MEGAFAC F-554 manufactured by DIC Co., Ltd., a fluorine-based surfactant, is 0.2 parts by mass, and 3-methoxybutyl of solvent The base acetate and propylene glycol monomethyl ether acetate were mixed to prepare a liquid composition (S-1) having a solid concentration of 15% by mass. At this time, the 3-methoxybutyl acetate content ratio was adjusted to 15% by mass in the total solvent.

The liquid composition (S-1) was applied onto a glass substrate by a slit coater, and then heated at 90 ° C for 100 seconds to pre-bake to form a coating film having a film thickness of 2.5 μm. Next, the substrate was cooled to room temperature, and then exposed to a exposure amount of 400 J/m ² through a photomask (slit width: 90 μm) using a high-pressure mercury lamp. Thereafter, the substrate was subjected to shower development by spraying with a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C for a period of 60 seconds under conditions of a developing pressure of 110 kPa and a developer flow rate of 1.2 liter/min. Thereafter, the substrate was washed with ultrapure water, air-dried, and then baked in a dust-free oven at 220 ° C for 30 minutes to form a pixel matrix in which the striped pixel patterns were arranged on the substrate.

The pixel pattern on the substrate was observed under an optical microscope, and it was confirmed whether or not the development residue on the unexposed portion of the substrate and the edge of the pattern were not damaged, and evaluated according to the following criteria. The evaluation results are shown in Table 1.

Evaluation basis for development residue

○: No development residue was found

×: development residue can be found

Evaluation criteria for pixel pattern defects

○: The pixel pattern defect is zero

△: The pixel pattern defect is one or more and less than 20

×: The pixel pattern defect is 20 or more

Next, the pixel pattern on the substrate was observed under an electron microscope, and the linearity of the pixel pattern was evaluated based on the following criteria. The evaluation results are shown in Table 1.

Linearity assessment benchmark

○: No minor defects were found on the edge of the pattern and part of the substrate was removed.

△: No part of the pattern edge was separated from the substrate, but minor defects were found.

×: Minor defects and parts of the substrate can be found at the edge of the pattern.

Examples 2 to 26 and Comparative Examples 1 to 9

In the same manner as in Example 1, except that the pigment dispersion liquid and the binder resin shown in Table 1 were changed, the liquid coloring compositions (S-2) to (S-35) were prepared.

Next, evaluation was carried out in the same manner as in Example 1 except that each of the liquid coloring compositions (S-2) to (S-35) was used instead of the liquid composition (S-1). The evaluation results are shown in Table 1.

The shorthand meanings in Table 1 are as follows.

C-1: In the formula (1-3), a ² + b ² = 6, each m is 12 in total, R ¹ is a hydrogen atom, and R ² is a compound of an ethyl group (trade name KAYARAD DPEA-12, Nippon Chemical Pharmaceutical Co., Ltd.)

C-2: In the formula (2-1), all of the six R are groups represented by the formula (2), n is 1, R ^{3 is} a hydrogen atom, and R ⁴ is a pentane-1,5-di Base compound (trade name KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd.)

C-3: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name KAYARAD MAX-3510, manufactured by Nippon Kayaku Co., Ltd.)

C-4: In the formula (1-2), four X ^{2 are a} group represented by the formula (1) or an acryloxy group, a ² + b ² = 4, each m is 4 in total, and R ¹ is hydrogen. Atom, R ² is a compound of an ethyl group (KAYARAD RP-1040, manufactured by Nippon Kayaku Co., Ltd.)

D-1: 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)butanone-1 (trade name IRGACURE 369, manufactured by BASF Corporation)

D-2: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) ( Trade name IRGACURE OX02, made by BASF)

D-3: 4,4'-bis(diethylamino)diphenyl ketone

D-4: ADEKA ARKLS NCI-831 (manufactured by ADEKA, Inc., O-acetyl oxime compound)

E-1: propylene glycol monomethyl ether acetate

E-2: 3-methoxybutyl acetate

Claims (6)

A colored composition comprising (A) a colorant, (B) a binder resin, and (C) a coloring composition of a polymerizable compound, characterized in that: (A) the content of the colorant is an all solid of the coloring composition 5 to 70% by mass of the component; and the following (C1) compound and (C2) compound are contained as (C) polymerizable compound: (C1) has three or more polymerizable unsaturated groups, and three or more polymerizable groups At least one of the unsaturated groups is a compound represented by the following formula (1); (C2) has two or more polymerizable unsaturated groups, and at least one of the two or more polymerizable unsaturated groups is as follows. a compound of the formula (2); [In the formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an exoethyl or propanediyl group, m represents an integer of 1 to 12, and "*" represents a linkage]; In the formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkanediyl group having 1 to 10 carbon atoms, n represents an integer of 1 to 5, and "*" represents a linkage. Wherein (C2) has two or more polymerizable unsaturated groups with respect to 100 parts by mass of the (B) binder resin, and at least one of the two or more polymerizable unsaturated groups is the above formula The content of the compound of the group (2) is 25 to 70 parts by mass. The coloring composition of claim 1, wherein the (C1) binder has at least three or more polymerizable unsaturated groups, and three or more of the polymerizable unsaturated groups are contained in an amount of 100 parts by mass of the (B) binder resin. The content of at least one compound of the group represented by the above formula (1) is from 1 to 70 parts by mass. The coloring composition of claim 1 or 2, further comprising (C3) as (C) a polymerizable compound; wherein the (C3) is a group represented by the above formula (1) and a group represented by the above formula (2) None of the polyfunctional (meth) acrylates. The coloring composition of claim 3, wherein the (C3) group represented by the above formula (1) and the group represented by the above formula (2) have no polyfunctional (meth) acrylate selected from the following a compound of at least one of (i) to (iii); (i) a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydric hydroxy compound with (meth)acrylic acid; (ii) a (meth) acrylate having a hydroxyl group a polyfunctional urethane (meth) acrylate obtained by reacting an ester with a polyfunctional isocyanate; (iii) a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a hydroxyl group-containing (meth) acrylate with an acid anhydride . A color filter having a coloring layer formed using the coloring composition of any one of claims 1 to 4. A display element comprising the color filter of claim 5.