JP2011137137A - Coloring composition, color filter and display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring composition suitable for an inkjet system, which forms a colored layer excellent in every property such as flatness, heat resistance, and solvent resistance. <P>SOLUTION: The coloring composition includes (A) a colorant, (B) a cross-linking agent, (C) a binder resin, (D) a fluorine-based surfactant having a hydroxy group, which is typically represented by formula (1), and (E) a solvent. The cross-linking agent (B) contains (b1) a compound having two or more N-alkoxymethyl amino groups. In formula (1), R<SP>21</SP>s each independently represents a 1-4C fluoroalkyl group, R<SP>22</SP>s each independently represents a methyl or ethyl group, and n is an integer of 2-100. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a colored composition, a color filter, and a display element. More specifically, the present invention relates to a color filter used for a transmissive or reflective color liquid crystal display device, a color imaging tube element, an organic EL display element, electronic paper, and the like. The present invention relates to a colored composition used for forming a useful colored layer, a color filter having a colored layer formed from the colored composition, and a display element including the color filter.

  Conventionally, in producing a color filter using a colored radiation-sensitive composition, after applying the colored radiation-sensitive composition on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed and drying, A method of obtaining pixels of each color by irradiating a dry coating film with a desired pattern shape (hereinafter referred to as “exposure”) and developing it is known (see, for example, Patent Document 1 and Patent Document 2). ing. A method of forming a black matrix using a photopolymerizable composition containing a black material (see, for example, Patent Document 3) is also known. Furthermore, a method for obtaining pixels of each color by an ink jet method using a colored thermosetting resin composition is also known (for example, see Patent Document 4).

  Various studies (for example, refer to Patent Document 5) are performed on the coloring composition used for forming pixels by an inkjet method from the viewpoint of ejection stability, storage stability, and flatness of formed pixels. It has been broken. However, an inkjet coloring composition having comprehensively excellent performance including the heat resistance and solvent resistance of the pixel has not been developed yet.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2006-299090 A

  The subject of this invention is providing the coloring composition suitable for an inkjet system which can form the colored layer excellent in all performances, such as flatness, heat resistance, and solvent resistance.

  As a result of diligent research, the present inventors have found that the above-mentioned problems can be solved by using a specific crosslinking agent and a specific surfactant in combination, and have completed the present invention.

  That is, the present invention contains (A) a colorant, (B) a crosslinking agent, (C) a binder resin, (D) a fluorine-containing surfactant having a hydroxyl group, and (E) a solvent, and (B) a crosslinking agent. (B1) It contains a compound having two or more N-alkoxymethylamino groups, and provides a colored composition.

  Moreover, this invention provides the color filter provided with the colored layer formed using the said coloring composition, and the display element which comprises the said color filter. Here, the “colored layer” means each color pixel, black matrix, etc. used in the color filter.

  According to the coloring composition of the present invention, a pixel excellent in flatness, heat resistance, and solvent resistance can be formed by an inkjet method. Moreover, surprisingly, the pixels formed using the colored composition of the present invention have high luminance and contrast ratio.

  Accordingly, the colored composition of the present invention includes color filters for color liquid crystal display elements in the electronic industry, color separation color filters for solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. It can be used very suitably for the production of various color filters.

  Hereinafter, the present invention will be described in detail.

Coloring composition- (A) Coloring agent-
The (A) colorant in the present invention is not particularly limited as long as it has colorability, and the color and material can be appropriately selected according to the application. Specifically, any of pigments, dyes and natural pigments can be used as the colorant. However, since the color filter is required to have heat resistance, the colorant in the present invention may be an organic pigment or an inorganic pigment. Pigments are preferred.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (CI). Names can be mentioned.

C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211;
C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;

C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 272;
C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment Green 58.

  These organic pigments can be used alone or in admixture of two or more.

  In the present invention, the organic pigment can be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. The organic pigment is preferably used by refining primary particles by so-called salt milling. The salt milling method is disclosed in, for example, Japanese Patent Application Laid-Open No. 08-179111.

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

  These colorants may be used by modifying the particle surface with a resin, if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. As a resin coating method on the carbon black surface, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be employed.

  The above colorants can be used alone or in admixture of two or more.

  When the colored composition of the present invention is used for forming a pixel, since the pixel is required to have high-definition color development, the colorant (A) is preferably a colorant having high color developability, specifically an organic pigment. Is preferably used.

  On the other hand, when the colored composition of the present invention is used for forming a black matrix, since the black matrix is required to have a light shielding property, an organic pigment or carbon black is preferably used as the (A) colorant.

By the way, a blue pixel formed by using a coloring composition containing a blue colorant, particularly a blue pigment, causes yellowing of the binder resin component or the crosslinking agent component or the blue pigment itself by heating at a high temperature during the post-baking process. There is a problem that transparency and color characteristics are deteriorated due to crystal transition and the like.
Further, a pixel formed using a coloring composition containing a coloring agent having an azo bond has a problem that the azo bond is decomposed by high-temperature heating during the post-baking process, and the color purity is lowered. Examples of the colorant having an azo bond include C.I. I. Pigment Yellow 150, monoazo pigments represented by pigments disclosed in JP-A No. 2001-354869, C.I. I. Disazo pigments such as CI Pigment Red 242 can be mentioned. Among them, monoazo pigments are easily discolored by heating at high temperatures. Among monoazo pigments, a molecular compound composed of a compound represented by the following formula (I) or a tautomer thereof and a compound represented by the following formula (II), particularly represented by the following formula (I): An inclusion compound comprising a compound or a host which is a tautomer thereof and a guest represented by the following formula (II) (hereinafter sometimes referred to as “specific yellow pigment”) is excellent in transparency and color purity. Yellow pigment, but easily discolored by high temperature heating.
The coloring composition of the present invention surprisingly solves the above heat resistance problem.

(In Formula (II), R ^{a to} R ^c each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group.)
The coloring composition of the present invention surprisingly solves the above heat resistance problem.

  In addition, C.I. I. A green pixel formed by using a halogenated zinc phthalocyanine pigment typified by CI Pigment Green 58 has a problem that when it is exposed to an organic solvent, the color components are eluted and the color purity is lowered. The colored composition of the present invention surprisingly solves the above solvent resistance problem.

  In the present invention, the content ratio of (A) the colorant is 5 to 70% by mass in the total solid content of the colored composition from the viewpoint of forming a pixel having excellent transparency and color purity or a black matrix having excellent light shielding properties. It is preferable that the content is 5 to 60% by mass. Here, solid content is components other than the solvent mentioned later.

  The colorant in the present invention can be used together with a dispersant and a dispersion aid as desired. As the dispersing agent, for example, an appropriate dispersing agent such as a cationic type, an anionic type, or a nonionic type can be used, and a polymer dispersing agent is preferable. Specifically, an acrylic copolymer, polyurethane, polyester, polyethyleneimine, polyallylamine, and the like can be given.

  Such a dispersant can be obtained commercially. For example, as an acrylic copolymer, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK Corporation (BYK)), As polyurethane, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (manufactured by Lubrizol Corp.), polyethylene As imine, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), As polyester, Azisper PB821, Azisper PB822, Azisper PB823, Jisupa PB824, Adisper PB827, Adisper PB880, Adisper PB881 (or more, Ajinomoto Fine-Techno Co., Ltd.), and the like.

  These dispersants can be used alone or in admixture of two or more. Content of a dispersing agent is 100 mass parts or less normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 1-70 mass parts, More preferably, it is 10-50 mass parts. In this case, when the content of the dispersant exceeds 100 parts by mass, the strength or the like of the resulting colored layer may be impaired.

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

-(B) Crosslinking agent-
In the present invention, the (B) crosslinking agent contains (b1) a compound having two or more N-alkoxymethylamino groups (hereinafter sometimes referred to as “crosslinking agent (b1)”). The cross-linking reaction of the cross-linking agent (b1) brings about excellent curability to the colored layer and also has excellent heat resistance to the colored layer because it has the property of hardly yellowing even with high-temperature heating.
The crosslinking agent (b1) is not particularly limited as long as it has two or more N-alkoxymethylamino groups. Examples thereof include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. it can. The “melamine structure, benzoguanamine structure” means a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the crosslinking agent (b1) include compounds represented by the following formulas (b1-1) to (b1-5).

In formula (b1-2), R ^{5 to} R ⁶ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms.
In the formula (b1-1) and the formulas (b1-3) to (b1-5), R ^{1 to} R ⁴ and R ^{7 to} R ²⁰ are each independently a hydrogen atom or a straight chain having 1 to 4 carbon atoms. A chain or branched alkyl group is shown. However, at least two of R ^{1 to} R ⁴ in Formula (b1-1), at least two of R ^{7 to} R ¹⁰ in Formula (b1-3), R ¹¹ to R ¹¹ in Formula (b1-4) At least two of R ¹⁶ and at least two of R ^{17 to} R ²⁰ in formula (b1-5) are linear or branched alkyl groups having 1 to 4 carbon atoms.
Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.

In the present invention, the crosslinking agent (b1) is preferably a compound having a melamine structure, a benzoguanamine structure or both from the viewpoint of solubility in a solvent, heat resistance of a pixel to be formed, and solvent resistance. A compound represented by (b1-4) or formula (b1-5) or a condensate thereof is preferred.
In this invention, a crosslinking agent (b1) can be used individually or in mixture of 2 or more types.

In the present invention, together with the crosslinking agent (b1), at least one selected from the group consisting of a polyfunctional (meth) acrylate having a carboxyl group and a polyfunctional (meth) acrylate having a hydroxyl group (hereinafter referred to as “crosslinking agent (b2) ) ”), The flatness of the colored layer can be improved.
Among the crosslinking agents (b2), the polyfunctional (meth) acrylate having a hydroxyl group is not particularly limited. For example, isocyanuric acid ethylene oxide-modified di (meth) acrylate, isocyanuric acid propylene oxide-modified di (meta) ) Acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, trimethylolpropane di (meth) acrylate, dipentaerythritol di (meth) acrylate, pentaerythritol tri (Meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol tetra (me ) Acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, and tripentaerythritol hepta acrylate.
In the present invention, the polyfunctional (meth) acrylate having a hydroxyl group is preferably a trifunctional or higher functional (meth) acrylate having a hydroxyl group, and particularly preferably pentaerythritol tri (meth) acrylate or dipentaerythritol penta (meth) acrylate. .

  Among the crosslinking agents (b2), the polyfunctional (meth) acrylate having a carboxyl group is not particularly limited. For example, the reaction between the polyfunctional (meth) acrylate having a hydroxyl group and an acid anhydride is performed. You can list things.

  Specific examples of acid anhydrides include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and the like, tribasic acid anhydrides. Trimellitic anhydride, etc., as tetrabasic acid dianhydride, pyromellitic anhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic acid Dianhydride, cyclopentanetetracarboxylic dianhydride, oxydiphthalic anhydride, ethylene glycol bisanhydro trimellitate, glycerin bis (anhydro trimellitate monoacetate), benzophenone tetracarboxylic dianhydride, methylcyclohexylene Tetracarboxylic dianhydride, etc. It can gel.

In the present invention, the polyfunctional (meth) acrylate having a carboxyl group is a tri- or higher functional (meth) acrylate, preferably having an acid value of 30 to 300 mgKOH / g, and preferably 50 to 250 mgKOH / g. Is more preferable. In particular, a reaction product of pentaerythritol tri (meth) acrylate and succinic anhydride and a reaction product of dipentaerythritol penta (meth) acrylate and succinic anhydride are preferable.

  In the present invention, the polyfunctional (meth) acrylate having a hydroxyl group and the polyfunctional (meth) acrylate having a carboxyl group can be used alone or in admixture of two or more. Of course, the polyfunctional (meth) acrylate which has a single or 2 or more types of hydroxyl group, and the polyfunctional (meth) acrylate which has a single or 2 or more types of carboxyl group can also be mixed and used.

In this invention, the content rate of a crosslinking agent (b1) is 5 mass% or more normally in all the crosslinking agents, Preferably it is 5-95 mass%, Most preferably, it is 10-90 mass%. Moreover, the content rate of a crosslinking agent (b2) becomes like this in all crosslinking agents, Preferably it is 1-80 mass%, Most preferably, it is 2-70 mass%. By using the crosslinking agent (b1) and the crosslinking agent (b2) in such an embodiment, a colored layer having excellent flatness, heat resistance and solvent resistance can be formed.

  In the present invention, other crosslinking agents can be used together with the crosslinking agent (b1) and the crosslinking agent (b2). Other crosslinking agents are not particularly limited, but polyfunctional (meth) acrylates having no hydroxyl group and carboxyl group are preferred. Specific examples of polyfunctional (meth) acrylates having no hydroxyl group and carboxyl group include aliphatic polyhydroxy compounds and esters of (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone, alkylene oxide modified Examples include polyfunctional (meth) acrylates, polyfunctional urethane (meth) acrylates obtained by reacting (meth) acrylates having a hydroxyl group with polyfunctional isocyanates.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and triglyceride. Trivalent or higher aliphatic polyhydroxy compounds such as pentaerythritol can be exemplified, and examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include the compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. Examples of polyfunctional (meth) acrylates include ethylene oxide and / or propylene oxide modified di (meth) acrylate of bisphenol A, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of isocyanuric acid, ethylene of trimethylolpropane Oxide and / or propylene oxide modified tri (meth) acrylate, pentaerythritol ethylene oxide and / or propylene oxide modified tetra (meth) acrylate, dipenta Risuritoru of ethylene oxide and / or propylene oxide-modified hexa (meth) acrylate, and the like.

  In the present invention, the other crosslinking agent is preferably a trifunctional or higher functional (meth) acrylate, particularly a 4-10 functional (meth) acrylate, from the viewpoint of the flatness, heat resistance, and solvent resistance of the pixel to be formed. Is preferred. Among them, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, polyfunctional urethane acrylate obtained by reacting dipentaerythritol pentaacrylate and diisocyanate is preferable.

  The total content of the (B) crosslinking agent in the present invention is preferably 5 to 1,000 parts by mass, more preferably 20 to 300 parts by mass with respect to 100 parts by mass of the (A) colorant. In this case, if the content of the crosslinking agent is too small, the strength and surface smoothness of the colored layer tend to be reduced. On the other hand, if the content is too large, the colorant concentration is relatively lowered, so that the desired color as a thin film It may be difficult to achieve the concentration.

  In the present invention, the total content of the crosslinking agent (b1) and the crosslinking agent (b2) is preferably 30% by mass or more, more preferably 40 to 95% by mass in the total crosslinking agent. By using each crosslinking agent in such an embodiment, the colored layer has excellent heat resistance, solvent resistance, and flatness.

-(C) Binder resin-
The (C) binder resin in the present invention is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as “carboxyl group-containing polymer”) is preferable, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). And a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as “unsaturated monomer (c2)”).

  Examples of the unsaturated monomer (c1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate and the like. These unsaturated monomers (c1) can be used alone or in admixture of two or more.

  In the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2), the copolymerization ratio of the unsaturated monomer (c1) is preferably 5 to 50% by mass, more preferably 10 to 10% by mass. 40% by mass. By copolymerizing the unsaturated monomer (c1) within such a range, a colored composition having excellent storage stability and alkali developability can be obtained.

Moreover, as said unsaturated monomer (c2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxy-α-methylstyrene;
Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (n = 2 -10) methyl ether (meth) acrylate, polypropylene glycol (n = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) ) Mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, G Serorumono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, such as unsaturated carboxylic acid ester of ethylene oxide-modified (meth) acrylate of p-cumylphenol;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.

  These unsaturated monomers (c2) can be used alone or in admixture of two or more.

  Specific examples of the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. Copolymers disclosed in JP-A-10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, and the like. Can be mentioned.

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

  The weight average molecular weight in terms of polystyrene (hereinafter sometimes referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the binder resin in the present invention is usually 1,000 to 300,000. , Preferably it is 3,000-100,000. If Mw is too small, the remaining film ratio of the resulting coating may decrease, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, the pattern shape will be impaired. There is a risk that the ink ejection properties may deteriorate.

  Further, the ratio (Mw / Mn) of the Mw of the binder resin in the present invention and the polystyrene-equivalent number average molecular weight (hereinafter sometimes referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran). ) Is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.

The binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

  In this invention, binder resin can be used individually or in mixture of 2 or more types.

  In this invention, content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. In this case, if the content of the binder resin is too small, for example, the storage stability and alkali developability of the resulting colored composition may be reduced. On the other hand, if the content is too large, the colorant concentration is relatively lowered. Therefore, it may be difficult to achieve a target color density as a thin film.

-(D) Fluorine-based surfactant having a hydroxyl group-
The colored composition of the present invention contains a fluorine-based surfactant having a hydroxyl group (hereinafter sometimes referred to as “surfactant (D)”). Since the surfactant (D) has a hydroxyl group, the affinity of the colored composition to the glass substrate is increased, and the spread of the coating is improved. It becomes possible to form. Further, it is considered that the curing reaction by thermal crosslinking between the hydroxyl group of the surfactant (D) and the N-alkoxymethylamino group of the crosslinking agent (b1) further enhances the solvent resistance and heat resistance of the colored layer.

  The surfactant (D) is not particularly limited as long as it is a fluorine-based surfactant having a hydroxyl group, but it may be a compound having a fluorinated alkyl group having 1 to 4 carbon atoms and two or more hydroxyl groups. preferable. As this surfactant, the compound represented by following formula (1) can be mentioned, for example.

(In Formula (1), R ²¹ independently represents a group having a fluorinated alkyl group having 1 to 4 carbon atoms, R ²² independently represents a methyl group or an ethyl group, and n Represents an integer of 2 to 100.)

In the above formula (1), R ²¹ is preferably a group having a C 1 to C 4 perfluoroalkyl group from the viewpoint of enhancing a desired effect, and in particular, CF ₃ CH ₂ —, CF ₃ CH ₂ CH _{2. -, CF 3 CF 2 CH 2} -, CF 3 CF 2 CH 2 CH 2 -, CF 3 CF 2 CF 2 CH 2 -, CF 3 CF 2 CF 2 CH 2 CH 2 -, CF 3 CF 2 CF 2 CF 2 CH ₂ — and CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ — are preferred.
Moreover, in said formula (1), it is preferable that n is 4-40. In this case, if n is too small, the flatness of the pixel may be deteriorated. On the other hand, if it is too large, the spread of the coloring composition on the substrate is deteriorated or the compatibility with other components is reduced. There is a risk of

The surfactant represented by the above formula (1) can be obtained commercially. For example, PF-636 commercially available from OMNOVA (in the above formula (1), R ²¹ is CF ₃ CH ₂ —, R ²² is a methyl group, the surfactant average value of n is 6), PF-6320 (the above formula (1) ^{R 21} in the _CF 3 _CH 2 ^{-, R 22} is a methyl group, the average value of n is 20 ), PF-656 (surfactant in which R ²¹ is CF ₃ CF ₂ CH ₂ —, R ²² is a methyl group, and n has an average value of 6 in the above formula (1)), PF-6520 (In the above formula (1), R ²¹ is CF ₃ CF ₂ CH ₂ —, R ²² is a methyl group, and the average value of n is 20).
In this invention, surfactant (D) can be used individually or in mixture of 2 or more types.

Content of surfactant (D) is 0.01-2.0 mass parts normally with respect to 100 mass parts of solid content except the solvent mentioned later, Preferably it is 0.02-1.5 mass parts, More preferably Is 0.05 to 1.0 part by mass. When there is too little content of surfactant (D), there exists a possibility that a desired effect may not be acquired, and when too large, there exists a possibility that roughening may arise on the colored layer surface.
In the present invention, known surfactants other than the surfactant (D), silicone surfactants, and the like can be used together with the surfactant (D) as the surfactant.

-(E) Solvent-
The colored composition of the present invention is usually prepared as a liquid composition by blending a solvent. As a solvent, as long as it has moderate volatility without dispersing or dissolving the components (A) to (D) constituting the colored composition and additive components described later, and reacting with these components, It can be appropriately selected and used.
When the colored composition of the present invention is used for forming a colored layer by an inkjet method, a solvent having a boiling point at 1 atm of preferably 180 ° C. or higher, more preferably a solvent of 200 ° C. to 290 ° C., particularly preferably 220 ° C. to A solvent having a temperature of 280 ° C. or lower (hereinafter also referred to as “high-boiling solvent”) is preferably 70% by mass or more, more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass in the total solvent. If the content of the high-boiling solvent is too small, not only the ink dischargeability is deteriorated because the colored composition is easily dried, but also the balance between the leveling speed and the drying speed of the colored composition is lost. The spread of the coloring composition on the substrate may also be deteriorated.

Examples of the high boiling point solvent include a solvent having two acetate structures represented by glycol diacetate such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;
Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol mono A solvent having one acetate structure such as phenyl ether acetate, propylene glycol butyl ether acetate, 3-methyl-3-methoxybutyl acetate;
Ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl 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, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, Benzylethyle Ter, dihexyl ether, diethylene glycol diethyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate , Propylene carbonate, N-methylpyrrolidone and the like.
Of these, from the viewpoint of dispersion stability of the coloring composition, a solvent having two acetate structures is preferable, glycol diacetate is more preferable, glycol diacetate having 2 to 6 carbon atoms is further preferable, and 1,3- Butylene glycol diacetate is particularly preferred.

  The high boiling point solvents can be used alone or in admixture of two or more.

  Moreover, when using the coloring composition of this invention for formation of the colored layer by an inkjet system, the solvent whose boiling point in 1 atmosphere is less than 180 degreeC can also be used together with a high boiling point solvent.

As a solvent having a boiling point of less than 180 ° C. at 1 atm, for example,
Alcohols such as methanol, ethanol, benzyl alcohol;
(Poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, erene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether;

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

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid -Propyl, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, pyruvate Esters such as ethyl, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl 2-oxobutyrate;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N, N-dimethylformamide and N, N-dimethylacetamide.

  Of these, benzyl alcohol, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene from the viewpoints of solubility, pigment dispersibility, etc. Glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate , 3-methoxybutyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate Methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl pyruvate are preferred.

  The above solvents having a boiling point of less than 180 ° C. at 1 atm can be used alone or in admixture of two or more.

  On the other hand, when the colored composition of the present invention is used for spin coating or slit die coating, a solvent having a boiling point at 1 atm of preferably less than 180 ° C, more preferably a solvent of 100 ° C to 180 ° C, particularly preferably 120 ° C to A solvent having a temperature of 180 ° C. or less is preferably 70% by mass or more, more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass in all the solvents.

  When the coloring composition of the present invention is used for spin coating or slit die coating, the solvent having a boiling point of less than 180 ° C. at 1 atm is the above-mentioned (poly) alkylene glycol monoalkyl ether, (poly) from the viewpoint of coating properties. Alkylene glycol monoalkyl ether acetate, ethers, ketones and esters are preferred, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene Glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, Lohexanone, n-butyl acetate, i-butyl acetate, i-pentyl acetate, 3-methoxybutyl acetate, n-butyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Particularly preferred.

  These solvents can be used alone or in admixture of two or more.

  The content of the solvent is preferably an amount such that the total concentration of each component excluding the solvent is 5 to 35% by mass from the viewpoint of ink discharge properties, coating properties, storage stability, and the like of the resulting colored composition. An amount of 30% by mass is more preferable.

-Photopolymerization initiator-
Radiation sensitivity can be imparted to the colored composition of the present invention by incorporating a photopolymerization initiator. The photopolymerization initiator in the present invention can generate active species capable of initiating the crosslinking reaction of the (B) crosslinking agent by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. A compound.

  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 -A diketone type compound, a polynuclear quinone type compound, a diazo type compound, an imide sulfonate type compound etc. can be mentioned.

  In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

  Among 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, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

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

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

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

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

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

  In this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  In this invention, content of a photoinitiator is 0.01-120 mass parts normally with respect to 100 mass parts of (B) crosslinking agents, Preferably it is 1-100 mass parts.

-Additive component-
The resin composition of the present invention can further contain various additive components as necessary.

As the additive component, for example,
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl-methyl-dimethoxysilane, N- (2-aminoethyl) -3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Adhesion promoters such as 3-chloropropyl-methyl-dimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;

Antioxidants such as 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones;
Anti-agglomeration agents such as sodium polyacrylate;
Thermal radical generators such as 1,1′-azobis (cyclohexane-1-carbonitrile), 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile;
Examples thereof include inkjet discharge performance stabilizers such as methanol, ethanol, i-propanol, n-butanol, and glycerin.

  Furthermore, the coloring composition of the present invention can contain a thermal acid generator. The thermal acid generator is a component that generates an acid by heating, and examples thereof include onium salts such as sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts. Of these thermal acid generators, sulfonium salts and benzothiazolium salts are preferred.

  Specific examples of the sulfonium salt and the benzothiazolium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, 4-hydroxyphenyl benzyl methylsulfonium hexafluoroantimonate, 4-acetoxyphenyl benzyl methylsulfonium hexamonate. Examples thereof include fluoroantimonate, 4-hydroxyphenyldibenzylsulfonium hexafluoroantimonate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, and 3-benzylbenzothiazolium hexafluoroantimonate.

  The said thermal acid generator can be used individually or in mixture of 2 or more types.

  In the present invention, the coloring composition can be prepared by an appropriate method, for example, it can be prepared by mixing the components (A) to (E) together with other components optionally added. . As a preferred method for preparing a coloring composition, (A) a coloring agent is ground in (E) a solvent in the presence of a dispersant, optionally together with a part of component (C), for example, using a bead mill, a roll mill or the like. While mixing and dispersing to make a colorant dispersion, then add (B) to (D) components and, if necessary, additional (E) solvent and other components to this colorant dispersion. The method of preparing by mixing can be mentioned.

Color filter The color filter of the present invention has a colored layer formed using the colored composition of the present invention.

  As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, a liquid composition of the colored radiation-sensitive composition of the present invention in which a red colorant is dispersed is applied onto the substrate, followed by pre-baking to evaporate the solvent and form a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined arrangement.

  Then, using the liquid composition of each colored radiation-sensitive composition in which a green or blue colorant is dispersed, the liquid composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above. A green pixel array and a blue pixel array are sequentially formed on the same substrate. Thereby, a color filter in which a pixel array of the three primary colors of red, green and blue is arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  The black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method. Using the radiation-sensitive composition, it can be formed in the same manner as in the case of forming the pixel. The film thickness of the black matrix made of a metal thin film is usually 0.1 to 0.2 μm, while the film thickness of the resin black matrix formed using the black radiation-sensitive composition is about 1 μm.

  Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.

  In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

When applying a liquid composition of a radiation sensitive composition to a substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, etc. is adopted. In particular, a spin coating method and a slit die coating method are preferable.
Pre-baking is usually performed by combining vacuum drying and heat drying. The vacuum drying is usually performed at 0.1 to 1 Torr. Moreover, the conditions of heat drying are 70-110 degreeC normally for about 1 to 10 minutes.

  The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm, as the film thickness after drying.

  Examples of the radiation light source used in forming the color filter include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, and argon ions. Laser light sources such as laser, YAG laser, XeCl excimer laser, nitrogen laser and the like can be mentioned, and radiation having a wavelength in the range of 190 to 450 nm is preferable.

Exposure of radiation is preferably 10~10,000J / ^{m 2.}

  Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.

  An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.

  As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

  The post-baking conditions are usually about 180 to 280 ° C. and about 20 to 40 minutes.

  The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

As a second method for producing a color filter, a method for obtaining pixels of each color by an ink jet method, which is disclosed in JP-A-7-318723, JP-A-2000-310706, and the like, is also known. In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, a liquid composition of the colored composition of the present invention in which a red colorant is dispersed in the formed partition wall is ejected by an inkjet apparatus, and then prebaked to evaporate the solvent. Next, this coating film is exposed as necessary and then cured by post-baking to form a red pixel pattern.
Next, using a liquid composition of each coloring composition in which a green or blue colorant is dispersed, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.
In addition, the partition has not only a light shielding function but also a function for preventing the color composition of each color discharged in the section from being mixed, so that the film is a film compared to the black matrix used in the first method described above. Thick. The film thickness is usually 1 to 3 μm. Therefore, a partition is normally formed using a black radiation sensitive composition.

The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. Thus, the film thickness of the pixel formed by the ink jet method is approximately the same as the thickness of the partition wall.
The coloring composition of the present invention can form a pixel having extremely excellent flatness without producing an unpainted portion in the partition wall by an ink jet method. Moreover, even if it is a case where it hardens | cures only by post-baking, the pixel which has the very outstanding solvent resistance can be formed. Moreover, since the pixel formed from the colored composition of the present invention has extremely excellent heat resistance, no deterioration in transparency and color characteristics is observed even when it is exposed to high-temperature post-baking. Therefore, the colored composition of the present invention is particularly suitable for forming a colored layer by an inkjet method.
Since the color filter of the present invention is excellent in transparency and color characteristics, it is extremely useful for a solid-state imaging device, an organic EL display device, electronic paper, etc. in addition to a transmissive or reflective color liquid crystal display device.

Display element The display element of the present invention comprises 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.

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

  Moreover, the organic EL display element provided with the color filter of the present invention can take an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.

  In addition, the electronic paper including the color filter of the present invention can adopt an appropriate structure, and examples thereof include a structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

  Hereinafter, the embodiments 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 colorant dispersion Preparation Example 1
(A) C.I. I. 13.0 parts by mass of Pigment Red 254, 7.5 parts by mass of Addisper PB880 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as a dispersant, and 79.5 parts by mass of 1,3-butylene glycol diacetate as a solvent by a bead mill The colorant dispersion (R1) was prepared by processing.

Preparation Example 2
(A) C.I. I. Pigment red 254 / C.I. I. Pigment Red 177 / specific yellow pigment in which the guest represented by the above formula (II) is melamine = 13.0 parts by mass of a 25/47/28 (mass ratio) mixture, Ajisper PB880 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as a dispersant 7.5 parts by mass and (E) 79.5 parts by mass of 1,3-butylene glycol diacetate as a solvent were processed by a bead mill to prepare a colorant dispersion (R2).

Preparation Example 3
(A) C.I. I. Pigment red 242 / C.I. I. Pigment Red 177 = 40/60 (mass ratio) 13.0 parts by mass of the mixture, 7.5 parts by mass of Ajisper PB880 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as the dispersant, and 1,3-butylene glycol diacetate as the solvent (E) 79.5 parts by mass were treated with a bead mill to prepare a colorant dispersion (R3).

Preparation Example 4
(A) C.I. I. Pigment Green 58 / specific yellow pigment in which the guest represented by the above formula (II) is melamine = 13.0 parts by mass of a 60/40 (mass ratio) mixture, and Azisper PB881 (manufactured by Ajinomoto Fine Techno Co., Ltd.) 6 .9 parts by mass and (E) 80.1 parts by mass of 1,3-butylene glycol diacetate as a solvent were processed by a bead mill to prepare a colorant dispersion (G1).

Preparation Example 5
(A) C.I. I. Pigment Green 36 / specific yellow pigment in which the guest represented by the above formula (II) is melamine = 13.0 parts by mass of 65/35 (mass ratio) mixture, and Ajisper PB881 (manufactured by Ajinomoto Fine Techno Co., Ltd.) 6 .9 parts by mass and (E) 80.1 parts by mass of 1,3-butylene glycol diacetate as a solvent were processed by a bead mill to prepare a colorant dispersion (G2).

Preparation Example 6
(A) C.I. I. Pigment Blue 15: 6 / C.I. I. Pigment Violet 23 = 83/17 (mass ratio) 12.0 parts by mass of the mixture, 6.8 parts by mass of Ajisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as the dispersant, and 1,3-butylene glycol diacetate as the solvent (E) 81.2 parts by mass were processed by a bead mill to prepare a colorant dispersion (B1).

Synthetic condenser tube of binder resin, flask equipped with stirrer was charged with 3 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of diethylene glycol monobutyl ether acetate, followed by 10 parts by weight of methacrylic acid, N-phenylmaleimide 25 parts by mass, 15 parts by mass of styrene, 40 parts by mass of diethylene glycol methyl ether methacrylate (manufactured by NOF Corporation, trade name: Blenmer ^R PME-100), 10 parts by mass of dicyclopentenyl acrylate, and α-methylstyrene dimer as a molecular weight regulator 5 parts by mass was charged, and nitrogen substitution was performed. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a binder resin solution (solid content concentration = 29.8%). The obtained binder resin was Mw = 8,200 and Mn = 3300. This binder resin solution is designated as “resin solution 1”.

Example 1
(A) 567 parts by weight of a colorant dispersion (R1) as a colorant, and a crosslinking agent mainly comprising a compound in which R ^{11 to} R ^{16 in} the above formula (b1-4) are all methyl groups as a crosslinking agent (b1) (Sanwa Chemical Co., Ltd., trade name MW-30, weight average polymerization degree 1.3) 25 parts by mass, as a crosslinking agent (b2) 7 parts by mass of a reaction product of dipentaerythritol pentaacrylate and succinic anhydride, other 18 parts by mass of dipentaerythritol hexaacrylate as a crosslinking agent, 111 parts by mass of resin solution 1 as (C) binder resin, and PF-6520 manufactured by OMNOVA as a surfactant (D) (in the above formula (1), R ²¹ is CF ₃ CF ₂ CH ₂ ^-, surfactants ^{R 22} is a methyl group, the average value of n is 20) 0.6 parts by weight, and 1,3-butylene glycol Zia cetearyl as solvent By mixing the door 272 parts by mass, coloring composition (IJ-1) was prepared.

  The coloring composition (IJ-1) was evaluated in the following manner. The evaluation results are shown in Table 3.

Evaluation of color characteristics The colored composition (IJ-1) was applied on a soda glass substrate using a spin coater, then vacuum dried at 0.2 Torr, and prebaked on a hot plate at 90 ° C. for 5 minutes. Further, post-baking was performed for 30 minutes in a clean oven at 230 ° C. to form a cured film.

  About the obtained cured film, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), a C light source, a chromaticity coordinate value (x, y) and a stimulus value (Y) in the CIE color system in a 2-degree field of view. Was measured. Moreover, the contrast ratio was measured about the obtained cured film using the contrast meter (Akasaka Electric Co., Ltd. CT-1, blank 20000). Moreover, the film thickness of the obtained cured film was measured using the alpha step IQ made from KLA-Tencor.

Evaluation of solvent resistance The glass substrate formed with the evaluation of the color characteristics and having a cured film formed thereon was cut into a 2 cm × 4 cm square to prepare a test piece. The obtained test piece was immersed in N-methylpyrrolidone at 25 ° C. for 30 minutes, and the color change ΔEab ^* before and after the immersion was determined. The solvent resistance is good when ΔEab ^* is less than 3, and very good when it is less than 2.5.

Evaluation of heat resistance The glass substrate formed with the evaluation of the color characteristics and having a cured film formed thereon was cut into a 2 cm × 4 cm square to prepare a test piece. The obtained test piece was heated in a clean oven at 250 ° C. for 1 hour, and the color change ΔEab ^* before and after heating was determined. The heat resistance is good when ΔEab ^* is less than 5, and is very good when it is less than 3.

Evaluation of pixel flatness and spreadability After drying using a inkjet printer Nanoprinter-1500S (manufactured by Microjet Co., Ltd.) in pixels partitioned by a partition wall having a height of 2.0 μm, a length of 500 μm and a width of 150 μm. The coloring composition was discharged so that the film thickness in the vicinity of the pixel center was 2.0 μm. After vacuum drying at 0.2 Torr, pre-baking was performed on a 90 ° C. hot plate for 5 minutes, and further post-baking was performed in a 230 ° C. clean oven for 30 minutes. Using α-step IQ (manufactured by KLA Tencor), the film thickness at the center of the pixel was measured in the width direction and the length direction.

  At this time, ΔH = A− (B + C) / 2 was obtained by setting A as the maximum value of the film thickness in the width direction and B and C as the film thickness at both ends of the pixel. The flatness of the pixel is good if this value is less than 0.60 μm, and very good if it is less than 0.40 μm.

  Further, the horizontal distance ΔL from the point having the maximum film thickness in the length direction and closest to the pixel end to the pixel end was measured. The spreadability of the pixel is good when this value is 50 μm or less, and extremely good when this value is 30 μm or less.

Evaluation of viscosity The viscosity (25C) of the colored composition was measured using an ELD viscometer manufactured by Tokyo Keiki Co., Ltd.

Evaluation of surface tension The surface tension of the colored composition was measured using a dynamometer (BYK-Gardner GmbH).

Examples 2-24 and Comparative Examples 1-10
Resin compositions (IJ-2) to (IJ-34) were prepared in the same manner as in Example 1, except that the types and amounts of the constituent components were changed as shown in Table 1. The respective compositions are shown in Table 1 and Table 2.

  Subsequently, evaluation was performed in the same manner as in Example 1 except that the resin compositions (IJ-2) to (IJ-34) were used in place of the resin composition (IJ-1). The evaluation results of Examples 1 to 24 are shown in Table 3. The evaluation results of Comparative Examples 1 to 10 are shown in Table 4.

Each component in Table 1 and Table 2 is as follows.
MW-30: a cross-linking agent mainly composed of a compound in which R ^{11 to} R ^{16 in the} formula (b1-4) are all methyl groups (manufactured by Sanwa Chemical Co., Ltd., trade name MW-30, weight average polymerization degree 1. 3)
BX-4000: a cross-linking agent mainly composed of a compound in which R ^{17 to} R ^{20 in} the above formula (b1-5) are all methyl groups (manufactured by Sanwa Chemical Co., Ltd., trade name: BX-4000, weight average polymerization degree: 1. 2)
b2-1: reaction product of dipentaerythritol pentaacrylate and succinic anhydride b2-2: dipentaerythritol pentaacrylate
b3-1: Dipentaerythritol hexaacrylate PF-6520: a surfactant (OMNOVA) in which R ²¹ is CF ₃ CF ₂ CH ₂ —, R ²² is a methyl group, and n has an average value of 20 in the above formula (1) Made)
PF-6320: Surfactant (manufactured by OMNOVA) in which R ²¹ is CF ₃ CH ₂ —, R ²² is a methyl group, and the average value of n is 20 in the above formula (1)
PF-656: Surfactant (manufactured by OMNOVA) in which R ²¹ is CF ₃ CF ₂ CH ₂ —, R ²² is a methyl group, and the average value of n is 6 in the above formula (1)
PF-636: Surfactant (manufactured by OMNOVA) in which R ²¹ is CF ₃ CH ₂ —, R ²² is a methyl group, and the average value of n is 6 in the above formula (1)
F475: Fluorine-based surfactant having no hydroxyl group (manufactured by DIC)
1,3-BGDA: 1,3-butylene glycol diacetate

  As is clear from Tables 1 to 4, the coloring composition of the present invention, in which the crosslinking agent (b1), which is a compound having two or more N-alkoxymethylamino groups, and a fluorine-containing surfactant having a hydroxyl group are used in combination. It can be seen that the product can form a pixel having excellent spreadability, pixel flatness, heat resistance, and solvent resistance by the inkjet method. Moreover, the pixel obtained by using the coloring composition of the present invention has high luminance and contrast ratio.

Claims (8)

  (A) a colorant, (B) a crosslinking agent, (C) a binder resin, (D) a fluorine-containing surfactant having a hydroxyl group, and (E) a solvent, and (B) the crosslinking agent is (b1) 2 A coloring composition comprising a compound having at least one N-alkoxymethylamino group. The (B) crosslinking agent further contains at least one selected from the group consisting of (b2) a polyfunctional (meth) acrylate having a carboxyl group and a polyfunctional (meth) acrylate having a hydroxyl group. The coloring composition according to 1.   The coloring composition according to claim 1 or 2, wherein the (D) fluorine-containing surfactant having a hydroxyl group is a compound having a fluorinated alkyl group having 1 to 4 carbon atoms and two or more hydroxyl groups. The coloring composition of Claim 3 whose said (D) fluorine-type surfactant which has a hydroxyl group is a compound represented by following formula (1).

(In Formula (1), R ²¹ independently represents a group having a fluorinated alkyl group having 1 to 4 carbon atoms, R ²² independently represents a methyl group or an ethyl group, and n Represents an integer of 2 to 100.) The coloring composition according to any one of claims 1 to 4, wherein the compound having (b1) two or more N-alkoxymethylamino groups is a compound having a melamine structure, a benzoguanamine structure, or both of them.   The coloring composition of any one of Claims 1-5 used for formation of the colored layer by an inkjet system.   The color filter provided with the colored layer formed using the coloring composition of any one of Claims 1-6.   A display element comprising the color filter according to claim 7.