JP6740705B2 - Coloring composition for color filter material, colored cured film for color filter material, color filter, display element and light receiving element - Google Patents

Description

The present invention relates to a colored composition for a color filter material, a colored cured film for a color filter material, a color filter, a display element and a light receiving element, and more specifically, a transmissive or reflective color liquid crystal display element, a light receiving element, an organic material. A colored composition suitably used for producing a colored cured film for a color filter material used in an EL display element, electronic paper, etc., a colored cured film formed using the colored composition, and the colored cured film. The present invention relates to a color filter, a display element, and a light receiving element.

In producing a color filter using the colored radiation-sensitive composition, on the substrate, after coating the pigment-dispersed colored radiation-sensitive composition and drying, the dried coating film is irradiated with radiation in a desired pattern shape. There is known a method of obtaining pixels of each color by irradiating (hereinafter referred to as “exposure”) and developing (for example, see Patent Documents 1 and 2). Further, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (see, for example, Patent Document 3) is also known. Furthermore, a method of obtaining pixels of each color by an inkjet method using a pigment-dispersed colored resin composition (see, for example, Patent Document 4) is also known.

In recent years, there has been a strong demand for higher contrast of liquid crystal display elements and higher definition of solid-state image pickup elements, and in order to realize these, application of dyes as colorants is being studied. However, generally speaking, compared to the case where a pigment is applied as a colorant, when a dye is applied, problems such as heat resistance and solvent resistance often occur.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A

An object of the present invention is to provide a colored composition for a color filter material suitable for forming a colored cured film for a color filter material having high heat resistance. Further, an object of the present invention is to provide a colored cured film formed using the colored composition, and a color filter, a display element, and a light receiving element including the colored cured film.

The inventors of the present invention have conducted intensive studies in view of such circumstances, and have found that the above problems can be solved by using a compound having a specific structure as a colorant, and have completed the present invention. ..
That is, the present invention provides a coloring composition for a color filter material containing (A) a colorant, (B) a binder resin and (C) a polymerizable compound, wherein the (A) colorant has the following formula (1). It is intended to provide a coloring composition for a color filter material, which contains the represented compound (hereinafter, also referred to as “specific coloring agent”).

[In the formula (1),
n represents an integer of 1 or more,
R ¹ and R ² each independently represent a hydrogen atom, a monovalent organic group or a cyano group, and when n is an integer of 2 or more, a plurality of R ¹ and R ² are the same or different. Well,
R ¹¹ , R ¹² and R ²¹ each independently represent a monovalent organic group.
However,
When n is 1, R ¹ and R ¹¹ may together form a ring structure, and R ² and R ²¹ may together form a ring structure,
When n is an integer of 2 or more, ^one of plural R ¹ s and R ¹¹ may be combined to form a ring structure, and one of plural R ^{1 s} and one of plural R ² s are the same. To form a ring structure. ]
Further, the present invention provides a colored cured film for a color filter material containing a specific colorant, and a color filter, a display element and a light receiving element having the colored cured film.

By using the colored composition of the present invention, a colored cured film having high heat resistance can be formed. Therefore, the colored composition of the present invention can be very suitably used for producing a display element such as a color liquid crystal display element, an organic EL display element, electronic paper, or a light receiving element such as a solid-state image pickup element.

Hereinafter, the present invention will be described in detail.
Coloring Composition Hereinafter, the constituent components of the coloring composition of the present invention will be described in detail.
-(A) Colorant-
The coloring composition of the present invention contains a specific colorant as the (A) colorant.

n represents an integer of 1 or more, preferably 1 to 3, more preferably 1 to 2, and even more preferably 2.

The monovalent organic group (excluding cyano group) in R ¹ , R ² , R ¹¹ , R ¹² and R ²¹ is a monovalent hydrocarbon group, a monovalent heterocyclic group or a monovalent organic group. At least one selected from the group consisting of a hydrocarbon group or a monovalent heterocyclic group, a linking group containing an atom other than a carbon atom or a hydrogen atom, a divalent hydrocarbon group and a divalent heterocyclic group; A group formed by combining with a valent group can be mentioned.

Examples of the monovalent hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Here, in the present specification, the “alicyclic hydrocarbon group” is a concept excluding an aliphatic hydrocarbon group having no cyclic structure. Further, in the present specification, the “alicyclic hydrocarbon group” and the “aromatic hydrocarbon group” include not only a group consisting of a ring structure but also a group in which an aliphatic hydrocarbon group is further substituted on the ring structure. It is a concept that also includes, and it is sufficient that at least an alicyclic hydrocarbon or aromatic hydrocarbon is included in the structure.

The aliphatic hydrocarbon group may be in the form of a straight chain or a branched chain, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group and an alkynyl group. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable. Specific examples of the alkyl group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, Examples thereof include an octyl group, a 2-ethylhexyl group, a decyl group and a dodecyl group. Moreover, as an alkenyl group, a C2-C20 alkenyl group is preferable, a C2-C15 alkenyl group is preferable, and a C2-C10 alkenyl group is still more preferable. Specific examples of the alkenyl group, ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-ethyl-2-butynyl group, 2-octynyl group, Examples thereof include (4-ethynyl)-5-hexynyl group and 2-decynyl group. Moreover, as an alkynyl group, a C2-C20 alkynyl group is preferable, a C2-C15 alkynyl group is preferable, and a C2-C10 alkynyl group is more preferable. Specific examples of the alkynyl group include, for example, ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-ethyl-2-butynyl group, 2-octynyl group. Group, (4-ethynyl)-5-hexynyl group, 2-decynyl group and the like.

The alicyclic hydrocarbon group includes a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged ring hydrocarbon group, a spiro hydrocarbon group, a cyclic terpene hydrocarbon group and the like. The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 30 carbon atoms, more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and an alicyclic carbon group having 3 to 12 carbon atoms. A hydrogen group is more preferred. Specific examples of the alicyclic hydrocarbon group include, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, t-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, tricyclodecanyl group, decahydro-2. -Naphthyl group, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl group, pentacyclopentadecanyl group, isobornyl group, adamantyl group, dicyclopentanyl group, dicyclopentenyl group, tricyclo Examples thereof include a pentanyl group and a tricyclopentenyl group.

As the aromatic hydrocarbon group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable. Here, in the present specification, the “aryl group” refers to a monocyclic to tricyclic aromatic hydrocarbon group, for example, a phenyl group, a benzyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group. , Xylyl group, naphthyl group, anthryl group, phenanthryl group, azulenyl group, 9-fluorenyl group and the like.

The monovalent heterocyclic group is preferably a 3-membered to 10-membered monocyclic heterocyclic group, a condensed bicyclic heterocyclic group, or a condensed tricyclic heterocyclic group, and specifically, Alicyclic heterocycles such as oxiranyl group, oxetanyl group, pyrrolidinyl group, imidazolidinyl group, pyrazolidinyl group, morpholinyl group, theomorpholinyl group, piperidyl group, piperidino group, piperazinyl group, homopyrerazinyl group, 1,3-dioxolan-2-yl group Group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, quinolyl group, isoquinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, imidazolyl group, pyrazolyl group, triazoyl group, tetrazolyl group, thiazolyl group, benzothiazolyl group, oxazolyl group, Examples thereof include aromatic heterocyclic groups such as indolyl group, indazolyl group, benzimidazolyl group, phthalimido group, thienyl group, furyl group, pyranyl group, purinyl group and naphthopyrrolidyl group.
As the linking group containing an atom other than a carbon atom or a hydrogen atom, —O—, —S—, —CO—, —NR ^b — (R ^b represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). , —SO ₂ — and the like.

Examples of the divalent hydrocarbon group include groups obtained by removing one hydrogen atom from the monovalent hydrocarbon group, and more specifically, alkanediyl group, alkynediyl group, cycloalkylene group, cyclo Examples thereof include alkenylene group and arylene group.

Examples of the divalent heterocyclic group include groups obtained by removing one hydrogen atom from the monovalent heterocyclic group.

Examples of the ring structure formed by R ¹ and R ¹¹ together include a nitrogen-containing heterocycle, and specific examples include the nitrogen-containing heterocycle described below. Moreover, a benzene ring is mentioned as a ring structure formed by one of plural R ¹ 's and one of plural R ² 's existing together.

In the compound represented by the formula (1), when n is 1, R ² is preferably a cyano group, and when n is an integer of 2 or more, it is adjacent to —COR ²¹ among a plurality of R ^{2 s} present. R ² bonded to a carbon atom is preferably a cyano group.
The compound represented by the formula (1) is more preferably a compound represented by the following formula (2).

[In the formula (2),
R ^{2, R 12} and ^{R 21} has the same meaning as ^{R 2, R 12} and ^{R 21} in Formula (1),
m represents an integer of 1 or more,
R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group, and when m is an integer of 2 or more, a plurality of R ³ and R ² may be the same or different,
Ring Z ¹ represents a nitrogen-containing heterocycle. ]
m represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.
Examples of the monovalent organic group for R ³ and R ⁴ include the same monovalent organic groups for R ¹ , R ² , R ¹¹ , R ¹² and R ²¹ .
The nitrogen-containing heterocycle in the ring Z ¹ may be a monocyclic heterocycle or a polycyclic heterocycle. Further, it may be an unsaturated ring or a saturated ring. Furthermore, different heteroatoms (eg oxygen atom, sulfur atom) may be present in the ring. Examples of such a nitrogen-containing heterocycle include a pyrrolidine ring, a pyrazoline ring, a morpholine ring, a thiomorpholine ring, a piperidine ring, a piperazine ring, a homopiperazine ring, and a tetrahydropyrimidine ring. , Pyrazine ring, pyrimidine ring, pyridazine ring, quinoline ring, isoquinoline ring, phthalazine ring, quinoxaline ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, benzothiazole ring, oxazole ring, indole ring, indazole ring, Examples thereof include nitrogen-containing aromatic heterocycles such as benzimidazole ring, naphthopyrrolidine ring, benzoxazole ring and phthalimide ring. Of these, a nitrogen-containing aromatic heterocycle is preferable, and a naphthopyrrolidine ring is more preferable.
As the compound represented by the formula (1), a compound represented by the following formula (3) is more preferable.

[In Formula (3),
^{m, R 2} ~R ^4, R ¹² and ^{R 21, m} in the formula (1), and ^R 2 ^{~R 4, R 12} and ^{R 21} synonymous,
Q ¹ is ^{-CR 13 R 14 -, = CR} 13 -, - NR 15 -, = N -, - linking group selected from O- and -S- the group consisting or comprising a combination of the linking group 2 Indicates a valence group,
R ^{13 to} R ¹⁵ each independently represent a hydrogen atom or a monovalent organic group,
Ring Z ² represents an aromatic ring or a heterocycle. ]
Examples of the monovalent organic group for R ^{13 to} R ¹⁵ include the same monovalent organic groups for R ¹ , R ² , R ³ , R ⁴ , R ¹¹ , R ¹² and R ²¹ .
The aromatic ring in the ring Z ² is preferably a 1-3 ring aryl ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an acenaphthylene ring, a fluorene ring and an azulene ring. preferable. Moreover, as the heterocycle in the ring Z ² , the same ones as described above can be mentioned.

In the compound represented by the formula (2) and the compound represented by the formula (3), R ² is preferably a cyano group when m is 1, and a plurality of R ² is present when m is an integer of 2 or more. it is preferred ^{R 2} bonded to the carbon atom adjacent to the -COR ²¹ of R ² is a cyano group.

In the formulas (1) to (3), a monovalent organic group in R ¹ , R ² , R ³ , R ⁴ , R ¹¹ , R ¹² , R ^{13 to} R ¹⁵ and R ²¹ and a nitrogen-containing heterocycle in the ring Z ¹ . The ring, and the aromatic ring and heterocycle in the ring Z ² may further have a substituent. Examples of such a substituent include a cyano group, an amino group, a nitro group, a halo group, a carboxy group, a hydroxy group, a sulfamoyl group, a carbamoyl group and a sulfo group.

Among such specific colorants, R ²¹ in formulas (1) to (3) is —OR ²² (R ²² represents a hydrocarbon group having a polymerizable unsaturated group as a substituent). More preferable. Examples of the polymerizable unsaturated group include (meth)acryloyl group, vinyl group and allyl group. Moreover, as the hydrocarbon group constituting R ²² , the same ones as those exemplified as the monovalent hydrocarbon group can be mentioned.

Examples of such a specific colorant include the following compounds.

The coloring composition of the present invention may contain a colorant other than the specific colorant as the (A) colorant. Examples of such other colorants include pigments and dyes, and these other colorants may contain one kind or two or more kinds. When another colorant is contained, the pigment is preferably an organic pigment and the dye is preferably an organic dye from the viewpoint of obtaining a pixel having high brightness, contrast and tinting strength.

The organic dye is not particularly limited, and for example, a known dye in addition to a compound classified into Dye in the color index (CI; issued by The Society of Dyers and Colorists) is used. be able to. As such dyes, from the structural aspect of the chromophore, for example, triarylmethane dye, cyanine dye, xanthene dye, anthraquinone dye, azo dye, dipyrromethene dye, quinophthalone dye, coumarin dye, pyrazolone dye, quinoline dye, nitro. Examples thereof include dyes, quinonimine dyes, phthalocyanine dyes, squarylium dyes, and the like. Among them, triarylmethane dyes, cyanine dyes, xanthene dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are preferable from the viewpoint of heat resistance.

Examples of the organic pigments include compounds that are classified as pigments by the color index (CI; issued by The Society of Dyers and Colorists), and among them, the following color index (C.I. .) Numbered ones can be preferably used.
C. I. Pigment Red 166, C.I. I. Pigment Red 177, C.I. I. Pigment Red 224, C.I. I. Pigment Red 242, C.I. I. Pigment Red 254, C.I. I. Pigment Red 264, C.I. I. Pigment Red 279 and other red pigments;
C. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59 and other green pigments;
C. I. Pigment Blue 15:6, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 79, C.I. I. Pigment Blue 80 and other blue pigments;
C. I. Pigment Yellow 83, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 179, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 211, C.I. I. Pigment Yellow 215 and other yellow pigments;
C. I. Pigment Orange 38 and other orange pigments;
C. I. Pigment Violet 19, C.I. I. Pigment Violet 23 and other purple pigments.

In addition, the brominated diketopyrrolopyrrole pigment represented by the formula (Ic) of JP-A-2011-523433 can also be used as a red pigment. Further, JP 2001-081348 A, JP 2010-026334 A, JP 2010-191304 A, JP 2010-237384 A, JP 2010-237569 A, JP 2011-006602 A, The lake pigments described in JP 2011-145346 A and the like can be mentioned.

In the present invention, when the pigment is contained as the (A) colorant, the pigment can be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method or a combination thereof. .. If desired, the pigment may be used after its particle surface is modified with a resin. Examples of the resin that modifies the particle surface of the pigment include the vehicle resin described in JP-A-2001-108817 or various commercially available pigment dispersion resins. As the resin coating method for the carbon black surface, for example, the methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be adopted. The organic pigment may be used by making the primary particles fine by so-called salt milling. As the salt milling method, for example, the method disclosed in Japanese Patent Laid-Open No. 08-179111 can be adopted.

Further, in the present invention, when the pigment (A) contains a pigment, it may further contain at least one kind selected from known dispersants and dispersion aids.

Examples of known dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkylphenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. Dispersants, polyester-based dispersants, (meth)acrylic dispersants and the like can be mentioned, and as commercially available products, for example, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by Big Chemie (BYK)). ) Etc., (meth)acrylic dispersants, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by Big Chemie (BYK)), Solsperse 76500 (Lubrizol). Urethane-based dispersants such as Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), etc., Azisper PB821, Azisper PB822, Ajisper PB880, Azisper PB881 (above, Ajinomoto Fine Techno ( In addition to polyester-based dispersants (such as manufactured by BYK Co., Ltd.), BYK-LPN21324 (manufactured by BYK) can be used.

In the present invention, the dispersant may be used alone or in combination of two or more.

In the present invention, the content of the dispersant is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, further preferably 20 to 100 parts by mass, and further preferably 20 to 50 parts by mass with respect to 100 parts by mass of the pigment. Is more preferable.

Examples of the dispersion aid include pigment derivatives. Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinophthalone.

The content ratio of the (A) colorant is usually 5 to 70% by mass, preferably 5 to 60% by mass, more preferably in the solid content of the coloring composition from the viewpoint of forming pixels having high brightness and excellent coloring power. Is 10 to 50% by mass, and particularly preferably 20 to 50% by mass. Here, the solid content is a component other than the solvent described below.

When the coloring composition of the present invention includes both the dye and the pigment as the (A) colorant, the content ratio of the dye is 5% by mass or more based on the total amount of the colorant, from the viewpoint that the effect of the present invention can be more enjoyed. It is preferable that the amount is 10% by mass or more, more preferably 15% by mass or more. The coloring composition of the present invention may contain a dye alone as the (A) colorant. The coloring composition of the present invention has high heat resistance even when the content ratio of the dye to the solid content of the coloring composition is high or when the dye and the pigment are used in combination as the (A) colorant. It is possible to form a colored cured film having

-(B) Binder resin-
The binder resin of the present invention is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter, also referred to as “carboxyl group-containing polymer”) is preferable, and for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, “unsaturated monomer). And a copolymerizable ethylenically unsaturated monomer (hereinafter, also referred to as "unsaturated monomer (b2)"). .. The binder resin may be used alone or in combination of two or more.

Examples of the unsaturated monomer (b1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono[2-(meth)acryloyloxyethyl], and ω-carboxypolycaprolactone mono(meth). Examples thereof include acrylate and p-vinylbenzoic acid.

The unsaturated monomer (b1) can be used alone or in combination of two or more.

Further, as the unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl 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 (polymerization degree 2 -10) methyl ether (meth)acrylate, polypropylene glycol (polymerization degree 2 to 10) methyl ether (meth)acrylate, polyethylene glycol (polymerization degree 2 to 10) mono(meth)acrylate, polypropylene glycol (polymerization degree 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, Glycerol mono(meth)acrylate, 4-hydroxyphenyl(meth)acrylate, ethylene oxide-modified (meth)acrylate of paracumylphenol, glycidyl(meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, 3-[( (Meth)acrylic acid esters such as (meth)acryloyloxymethyl]oxetane and 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 ;
A macromonomer having a mono(meth)acryloyl group at the terminal of the polymer molecular chain such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane can be used.

The unsaturated monomer (b2) can be used alone or in combination of two or more.

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. , And more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition having excellent alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. 2000-56118, Japanese Patent Laid-Open No. 2004-101728, etc. We can list coalescence.

Further, 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, and As disclosed in Japanese Unexamined Patent Publication No. 2008-181095, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth)acryloyl group in a side chain can be used as a binder resin. In the colored composition of the present invention, a highly sensitive colored composition can be obtained by using a carboxyl group-containing polymer having a polymerizable unsaturated bond such as (meth)acryloyl group in the side chain as the binder resin. Moreover, it is preferable in that the curability of the coating film can be enhanced.

The binder resin in the present invention has an Mw measured by GPC of usually 1,000 to 100,000, preferably 3,000 to 50,000. By adopting such a mode, heat resistance can be further enhanced, and the transferability and the generation of foreign matter can be effectively suppressed.

Moreover, Mw/Mn of the binder resin is preferably 1.0 to 5.0, and more preferably 1.0 to 3.0. In addition, Mw and Mn here mean the polystyrene-equivalent number average molecular weight measured by GPC (elution solvent: tetrahydrofuran).

The binder resin can be produced by a known method, for example, by the method disclosed in JP 2003-222717 A, JP 2006-259680 A, WO 2007/029871 Pamphlet, etc. Its structure, Mw, and Mw/Mn can also be controlled.

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, and more preferably 50 to 200 parts by mass with respect to 100 parts by mass of the (A) colorant. .. With such an aspect, not only a colored cured film having excellent heat resistance can be formed, but also a pattern shape is excellent, and further, generation of precipitates and coating film foreign matters can be suppressed.

-(C) Polymerizable compound-
In the present invention, the polymerizable compound means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the (C) polymerizable compound is preferably a compound having two or more (meth)acryloyl groups or a compound having two or more N-alkoxymethylamino groups. The polymerizable compound (C) may be used alone or in combination of two or more.

Specific examples of the compound having two or more (meth)acryloyl groups include a polyfunctional (meth)acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth)acrylic acid, and a caprolactone-modified polyfunctional (meth)acrylate. ) Acrylate, alkylene oxide-modified polyfunctional (meth)acrylate, polyfunctional urethane (meth)acrylate obtained by reacting (meth)acrylate having a hydroxyl group with polyfunctional isocyanate, (meth)acrylate having a hydroxyl group and acid anhydride Examples thereof include a polyfunctional (meth)acrylate having a carboxyl group obtained by reacting a product.

Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and 3 such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. An aliphatic polyhydroxy compound having a valence of 3 or more can be mentioned. Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and glycerol diacrylate. Methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and the like. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and anhydrous dibasic acids such as hexahydrophthalic anhydride, pyromellitic dianhydride, and biphenyltetracarboxylic acid. Tetrabasic acid dianhydrides such as dianhydride and benzophenone tetracarboxylic acid dianhydride can be mentioned.

Examples of the caprolactone-modified polyfunctional (meth)acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. The alkylene oxide-modified polyfunctional (meth)acrylate includes at least one selected from bisphenol A di(meth)acrylate, ethylene oxide and propylene oxide modified with at least one selected from ethylene oxide and propylene oxide. Modified isocyanuric acid tri(meth)acrylate, modified with at least one selected from ethylene oxide and propylene oxide Modified with trimethylolpropane tri(meth)acrylate, modified with at least one selected from ethylene oxide and propylene oxide Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, Dipentaerythritol penta modified with at least one selected from ethylene oxide and propylene oxide Examples thereof include dipentaerythritol hexa(meth)acrylate modified with at least one selected from (meth)acrylate, ethylene oxide and propylene oxide.

Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, a urea structure, and the like. The melamine structure and the benzoguanamine structure refer to chemical structures having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and are concepts including melamine, benzoguanamine, and condensates thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N,N,N′,N′,N″,N″-hexa(alkoxymethyl)melamine and N,N,N′. , N′-tetra(alkoxymethyl)benzoguanamine, N,N,N′,N′-tetra(alkoxymethyl)glycoluril and the like can be mentioned.

Of these polymerizable compounds, a polyfunctional (meth)acrylate obtained by reacting an aliphatic polyhydroxy compound having a valence of 3 or more with (meth)acrylic acid, a caprolactone-modified polyfunctional (meth)acrylate, a polyfunctional urethane (Meth)acrylate, polyfunctional (meth)acrylate having a carboxyl group, N,N,N′,N′,N″,N″-hexa(alkoxymethyl)melamine, N,N,N′,N′ -Tetra(alkoxymethyl)benzoguanamine is preferred. Among polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate is a compound obtained by reacting pentaerythritol triacrylate and succinic anhydride among polyfunctional (meth)acrylates having a carboxyl group, and is obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and the generation of foreign matter is difficult.

The content of the (C) polymerizable compound in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 800 parts by mass, and 50 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. Is more preferable. By adopting such an embodiment, it is possible to form a pixel having excellent heat resistance and pattern shape, or a black matrix and a black spacer having excellent light shielding properties.

-Photopolymerization initiator-
The colored composition of the present invention may contain a photopolymerization initiator. This makes it possible to impart radiation sensitivity to the colored composition. The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating the polymerization of the polymerizable compound (C) upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam and X-ray. .. The photopolymerization initiator may be used alone or in combination of two or more.

Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -Diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, onium salt compounds and the like can be mentioned. Among them, at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds and O-acyl oxime compounds is preferable.

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

Further, specific examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1-(4- Examples thereof include morpholinophenyl)butan-1-one and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one.

In addition, specific examples of the biimidazole compound include 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole and 2,2′-. Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4 Examples include',5,5'-tetraphenyl-1,2'-biimidazole and the like.

When a biimidazole-based compound is used as the photopolymerization initiator, it is preferable to use a hydrogen donor in combination because the sensitivity can be improved. The "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of hydrogen donors include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; 4,4′-bis(dimethylamino)benzophenone and 4,4′-bis(diethylamino)benzophenone. The amine-based hydrogen donors can be mentioned. In the present invention, the hydrogen donors may be used alone or in combination of two or more, but one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. Is preferable in that the sensitivity can be further improved.

Specific examples of the triazine-based compound include compounds described in JP-B-57-6096 and JP-A-2003-238898, paragraphs [0063] to [0065].

Specific examples of O-acyl oxime compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), ethanone, 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. As a commercial product of the O-acyl oxime compound, NCI-831, NCI-930 (above, manufactured by ADEKA CORPORATION), OXE-01, OXE-02 (above, manufactured by BASF Corporation) and the like can also be used. ..

In the present invention, when a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound is used, a sensitizer may be used together. Examples of such a sensitizer include 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 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 the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, and more preferably 1 to 100 parts by mass with respect to 100 parts by mass of the (C) polymerizable compound. By adopting such a mode, not only the generation of foreign matter can be suppressed, but also curability and film characteristics can be improved.

-Solvent-
The coloring composition of the present invention contains the above-mentioned components (A) to (C) and optionally other components, and is usually prepared as a liquid composition by mixing an organic solvent. ..

As the organic solvent, as long as it is a solvent that disperses or dissolves the components (A) to (C) and other components constituting the coloring composition, does not react with these components, and has appropriate volatility, Can be selected and used. The solvent may be used alone or in combination of two or more.

Among such organic solvents, for example,
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, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di (Poly)alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo)alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;

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, (Poly)alkylene glycol monoalkyl ether acetate such as 3-methyl-3-methoxybutyl acetate;
Cyclic 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;
Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, and 3-methyl-3-methoxybutylpropionate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyrate -Fatty acid alkyl esters such as propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone, lactams and the like.

Among these solvents, at least one selected from (poly)alkylene glycol monoalkyl ether and (poly)alkylene glycol monoalkyl ether acetate is preferable from the viewpoint of solubility, pigment dispersibility, coatability, and the like.

The content of the solvent is not particularly limited, but the total concentration of each component of the coloring composition excluding the solvent is preferably 5 to 50% by mass, and 10 to 40% by mass. More preferable. With such an aspect, a colored composition having excellent dispersibility and stability and good coating properties can be obtained.

-Additives-
The coloring composition of the present invention may contain various additives, if necessary.

Examples of the additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylates); surfactants such as fluorine-based surfactants and silicone-based surfactants; vinyl. Trimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyl Adhesion promoters such as dimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis(4-methyl-6-t-butylphenol) , 2,6-di-t-butylphenol and other antioxidants; 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, alkoxybenzophenones and other UV absorbers; Anti-aggregation agents such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, Residue improvers such as 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid mono[2-(meth)acryloyloxy] Ethyl], phthalic acid mono[2-(meth)acryloyloxyethyl], ω-carboxypolycaprolactone mono(meth)acrylate, and the like may be mentioned.

Method for Preparing Colored Composition for Color Filter The colored composition of the present invention can be prepared by an appropriate method. Examples of the method for preparing the colored composition include components (A) to (C) as a solvent or optionally. It can be prepared by mixing with other ingredients to be added. When (A) the colorant contains a pigment, the pigment is mixed and dispersed in a solvent in the presence of a dispersant, optionally with (B) a part of the binder resin, for example, by using a bead mill, a roll mill or the like while pulverizing. To obtain a pigment dispersion liquid, and then, to this pigment dispersion liquid, the component (C), a photopolymerization initiator, if necessary, and an additional binder resin (B), a solvent and other components are added and mixed. The method of preparing by this is preferable.

Colored cured film for color filter and method for forming the same The colored cured film of the present invention contains a specific colorant as a colorant, but can be formed using the colored composition of the present invention. The colored cured film used for the color filter and the method for forming the same will be described below.

As a method of manufacturing a color filter, the following method can be mentioned first. First, if necessary, a light-shielding layer (black matrix) is formed on the surface of the substrate so as to partition the portions for forming pixels. Then, for example, a liquid composition of the blue radiation-sensitive coloring composition of the present invention is applied onto this substrate, and then prebaked to evaporate the solvent to form a coating film. Next, this coating film is exposed through a photomask and then developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Then, post-baking is performed to form a pixel array in which blue pixel patterns (colored cured film) are arranged in a predetermined array.

Then, using each green or red radiation-sensitive coloring composition, coating, pre-baking, exposure, development and post-baking of each radiation-sensitive coloring composition is carried out in the same manner as described above to obtain a green pixel array and a red pixel array. The pixel array of 1 is sequentially formed on the same substrate. As a result, a color filter in which pixel arrays of the three primary colors of blue, green and red are arranged on the substrate can be obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

The black matrix can be formed by forming a thin metal film of chromium or the like formed by sputtering or vapor deposition into a desired pattern by using a photolithography method, but it is radiation sensitive in which a black colorant is dispersed. It can also be formed using the coloring composition in the same manner as in the case of forming the pixel.

Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. If desired, these substrates may be subjected to appropriate pretreatments such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction method, vacuum deposition and the like.

When applying the radiation-sensitive 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 (slit coating method), or a bar coating method. However, it is particularly preferable to use a spin coating method or a slit die coating method.

Prebaking is usually at 70 to 110° C. for about 1 to 10 minutes.

The coating thickness is usually 0.6 to 8 μm, and preferably 1.2 to 5 μm as the film thickness after drying.

Examples of the radiation light source used when forming at least one selected from the pixel and the black matrix include, 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, and a low pressure. Examples thereof include a lamp light source such as a mercury lamp and a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. Radiation having a wavelength in the range of 190 to 450 nm is preferable.

The exposure dose of radiation is generally preferably 10 to 10,000 J/m ² .

Examples of the alkaline developer include sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene. An aqueous solution of 1,5-diazabicyclo-[4.3.0]-5-nonene or the like is preferable.

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. After the alkali development, it is usually washed with water.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid pour) developing method, or the like can be applied. The developing conditions are preferably room temperature and 5 to 300 seconds.

The post-baking condition is usually 180 to 280° C. and about 10 to 60 minutes.

The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

Further, as a second method of manufacturing a color filter, a method of obtaining pixels of each color by an inkjet method, which is disclosed in JP-A-7-318723, JP-A-2000-310706, or the like, can be adopted. .. In this method, first, a partition that also has a light-shielding function is formed on the surface of the substrate. Then, for example, a liquid composition of a blue thermosetting coloring composition is discharged into the formed partition wall by an inkjet device, and then prebaked to evaporate the solvent. Next, this coating film is exposed if necessary, and post-baked to cure it, thereby forming a blue pixel pattern.

Then, using each of the green or red thermosetting coloring compositions, a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate in the same manner as above. As a result, a color filter in which pixel patterns of the three primary colors of blue, green and red are arranged on the substrate can be obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

Incidentally, the partition wall not only has a light-shielding function, but also has a function of preventing the thermosetting coloring compositions of the respective colors discharged into the compartment from being mixed with each other, and therefore, compared with the black matrix used in the first method described above. , The film thickness is thick. Therefore, the partition wall is usually formed by using the black radiation-sensitive composition.

The substrate used for forming the color filter, the light source for radiation, and the prebaking and postbaking methods and conditions are the same as those in the first method described above. In this way, the film thickness of the pixel formed by the inkjet method is approximately the same as the height of the partition wall.

A protective film is formed on the pixel pattern thus obtained, if necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, spacers may be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but it may be a spacer having a light-shielding property (black spacer). In this case, a radiation-sensitive coloring composition in which a black coloring agent is dispersed is used, but the coloring composition of the present invention can also be suitably used for forming such a black spacer.

The coloring composition of the present invention can be suitably used in forming any colored cured film such as pixels for each color used in a color filter, a black matrix, and a black spacer. The color filter having the colored cured film of the present invention thus formed is extremely useful for color liquid crystal display devices, organic EL display devices, electronic papers, etc. because of its extremely high brightness and color purity. It should be noted that the color filter, display element and light receiving element described later may be those having at least one colored cured film containing the specific colorant of the present invention.

Color Filter The color filter of the present invention comprises the colored cured film of the present invention. Specifically, it may be any one provided with the colored cured film of the present invention as a member such as each color pixel used in a color filter, a black matrix, a black spacer or the like.

Display Element The display element of the present invention comprises the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, electronic paper and the like.

The color liquid crystal display device provided with the colored cured film of the present invention may be a transmissive type or a reflective type, and can have an appropriate structure. For example, a structure in which a color filter is formed on a substrate different from a driving substrate on which thin film transistors (TFTs) are arranged, and the driving substrate and the substrate on which the color filter is formed face each other with a liquid crystal layer in between. In addition, a substrate having a color filter formed on the surface of a driving substrate on which a thin film transistor (TFT) is arranged and a substrate having an ITO (tin-doped indium oxide) electrode formed thereon have a liquid crystal layer. It is also possible to adopt a structure in which they face each other. The latter structure has an advantage that the aperture ratio can be remarkably improved and a bright and high-definition liquid crystal display device can be obtained. When the latter structure is adopted, the black matrix or the black spacer may be formed on either the substrate side on which the color filter is formed or the substrate side on which the ITO electrode is formed.

The color liquid crystal display device including the colored cured film of the present invention may include a cold cathode fluorescent lamp (CCFL: Cold Cathode Fluorescent Lamp) and a backlight unit using a white LED as a light source. As the white LED, for example, a red LED, a green LED, and a blue LED are combined to obtain white light by mixing colors, and a blue LED, a red LED, and a green phosphor are combined to obtain white light by mixing colors, and a blue LED. A white LED that obtains white light by mixing colors by combining a red-emitting phosphor and a green-emitting phosphor, a white LED that obtains white light by mixing a blue LED and a YAG-based phosphor, a blue LED, an orange-emitting phosphor, and a green-emitting fluorescent Examples thereof include a white LED that obtains white light by mixing colors by combining the bodies, and a white LED that obtains white light by mixing colors by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor and a blue light emitting phosphor.

The color liquid crystal display device including the colored cured film of the present invention includes 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 (Optical) type. An appropriate liquid crystal mode such as a compensated birefringence type can be applied.

Further, the organic EL display device provided with the colored cured film of the present invention can have an appropriate structure, for example, the structure disclosed in JP-A No. 11-307242.

Further, the electronic paper provided with the colored cured film of the present invention can have an appropriate structure, and examples thereof include the structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

Light receiving element The light receiving element of the present invention comprises the colored cured film of the present invention.
The light-receiving element of the present invention may have an appropriate structure. For example, the colored cured film of the present invention is used as a color filter constituting a solid-state image sensor, and by combining it with a photodiode, an image sensor such as a solid-state image sensor can be obtained. Can be configured. Further, by using the colored cured film of the present invention as an infrared light transmission filter and combining it with a photodiode, an infrared light detection pixel can be formed.

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
As a colorant, C.I. I. 15 parts by mass of Pigment Green 58, 12.5 parts by mass of BYK-LPN21116 (manufactured by BYK Corporation) as a dispersant (solid content concentration=40% by mass), and 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent. A pigment dispersion liquid (a-1) was prepared by treating with a bead mill and then filtering with a Millipore filter having a pore size of 0.5 μm.

<Synthesis of binder resin>
Synthesis example 1
In a flask equipped with a cooling tube and a stirrer, 44 parts by mass of p-vinylbenzyl glycidyl ether, 40 parts by mass of N-phenylmaleimide and 16 parts by mass of benzyl methacrylate were dissolved in 300 parts by mass of propylene glycol monomethyl ether acetate, and further 2,2 8 parts by mass of'-azobisisobutyronitrile and 8 parts by mass of 2,4-diphenyl-4-methyl-1-pentene were charged, and the atmosphere was replaced with nitrogen. Then, the temperature of the reaction solution was raised to 80° C. with gentle bubbling and nitrogen bubbling, and this temperature was maintained to carry out polymerization for 5 hours.
Then, 17 parts by mass of methacrylic acid, 0.5 parts by mass of p-methoxyphenol and 4.4 parts by mass of tetrabutylammonium bromide were added to this reaction solution, and the reaction was carried out at a temperature of 120° C. for 9 hours. Furthermore, after adding 18.5 parts by mass of succinic anhydride and reacting at a temperature of 100° C. for 6 hours, the reaction solution was washed twice with the temperature kept at 85° C. and concentrated under reduced pressure to obtain a binder. A resin solution (solid content concentration=33% by mass) was obtained. The obtained binder resin had Mw=7,800 and Mn=5,000. This binder resin solution is referred to as "binder resin (B1) solution".

Example 1
By mixing 10 parts by mass of the compound represented by the formula (A-1) as a colorant and 90 parts by mass of ethyl lactate as a solvent, the mixture is filtered through a Millipore filter having a pore size of 0.5 μm to obtain a colorant solution (A -1) was prepared.
Next, 32.7 parts by mass of pigment dispersion liquid (a-1), 22.0 parts by mass of colorant solution (A-1), 12.2 parts by mass of binder resin (B1) solution as a binder resin, and as a polymerizable compound. Toagosei Co., Ltd. M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 6.0 parts by mass, 2,2'-bis(2-chlorophenyl)-4,4' as a photopolymerization initiator ,5,5'-Tetraphenyl-1,2'-biimidazole (Hodogaya Chemical Co., Ltd.) 1.2 parts by mass and 2-mercaptobenzothiazole (Tokyo Kasei Co., Ltd.) 0.4 parts by mass, fluorine-based surface active agent 0.04 parts by mass of Megafac F-554 manufactured by DIC Co., Ltd. as an agent and propylene glycol monomethyl ether acetate as a solvent were mixed. Then, a colored composition having a solid content concentration of 20 mass% was prepared by filtering with a Millipore filter having a pore diameter of 0.5 μm.

Evaluation of heat resistance The coloring composition was applied using a spin coater on a soda glass substrate on the surface of which a SiO ₂ film that prevents elution of sodium ions was formed, and then prebaked for 2 minutes on a hot plate at 90°C. Then, a coating film having a film thickness of 2.5 μm was formed. Next, after cooling this substrate to room temperature, the coating film was exposed to radiation having a wavelength of 365 nm, 405 nm, and 436 nm at an exposure amount of 400 J/m ² through a photomask using a high-pressure mercury lamp. Then, shower development was performed for 90 seconds on this substrate by discharging a developer consisting of 0.04 mass% potassium hydroxide aqueous solution at 23° C. at a developing pressure of 1 kgf/cm ² (nozzle diameter 1 mm). Then, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 200° C. for 30 minutes to form a dot pattern on the substrate. With respect to the obtained dot pattern, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), a chromaticity coordinate value (x, y) and a stimulus value (Y) in a CIE color system in a C light source and a 2 degree visual field. Was measured.

Next, after the substrate was additionally baked at 230° C. for 90 minutes, the chromaticity coordinate values (x, y) and the stimulus value (Y) were measured to evaluate the color change before and after the additional baking, that is, ΔE ^* _ab . .. As a result, when the value of ΔE ^* _ab is less than 1.5, it is “◎”, when it is 1.5 or more and less than 3.0, “◯”, and when it is 3.0 or more and less than 5.0, “Δ”, The case of 5.0 or more was evaluated as "x". The evaluation results are shown in Table 1. It can be said that the smaller the ΔE ^* _ab value, the better the heat resistance.

Examples 2-9 and Comparative Example 1
A colorant solution and a colorant composition were prepared in the same manner as in Example 1 except that the compound shown in Table 1 was used instead of the compound represented by formula (A-1) as the colorant. .. Next, heat resistance was evaluated in the same manner as in Example 1 using the obtained coloring composition. The results are shown in Table 1. The compound (A-10) used in Comparative Example 1 is as described below.

Claims (6)

A coloring composition for a color filter material, which comprises (A) a colorant, (B) a binder resin, and (C) a polymerizable compound,
(A) A coloring composition for a color filter material, wherein the coloring agent contains a compound represented by the following formula ( 3 ).
[In the formula ( 3 ),
m represents an integer of 1 or more,
R ² is water atom, a monovalent organic group or a cyano group, R ³ and R ⁴ are, independently of one another, a hydrogen atom or a monovalent organic group, and when m is 2 or greater , A plurality of R ³ and R ^{2 present} may be the same or different,
R ¹² and R ²¹ each independently represent a monovalent organic group.
Q ¹ is ^{-CR 13 R 14 -, = CR} 13 -, - NR 15 -, = N -, - O- and -S-
A connecting group selected from the group consisting of, or a divalent group formed by combining the connecting groups,
R ^{13 to} R ¹⁵ each independently represent a hydrogen atom or a monovalent organic group,
Ring Z ² represents an aromatic ring or a heterocycle. ] The colored composition for a color filter material according to claim 1 , wherein R ²¹ is —OR ²² (R ²² represents a hydrocarbon group having a polymerizable unsaturated group as a substituent). A colored cured film for a color filter material, comprising a compound represented by the following formula ( 3 ).
[In the formula ( 3 ),
m represents an integer of 1 or more,
R ² is water atom, a monovalent organic group or a cyano group, R ³ and R ⁴ are, independently of one another, a hydrogen atom or a monovalent organic group, and when m is 2 or greater , A plurality of R ³ and R ^{2 present} may be the same or different,
R ¹² and R ²¹ each independently represent a monovalent organic group.
Q ¹ is ^{-CR 13 R 14 -, = CR} 13 -, - NR 15 -, = N -, - O- and -S-
A connecting group selected from the group consisting of, or a divalent group formed by combining the connecting groups,
R ^{13 to} R ¹⁵ each independently represent a hydrogen atom or a monovalent organic group,
Ring Z ² represents an aromatic ring or a heterocycle. ] A color filter comprising the colored cured film for a color filter material according to claim 3 . A display device comprising the colored cured film for a color filter material according to claim 3 . A light-receiving element comprising the colored cured film for a color filter material according to claim 3 .