JP2010085769A - Red curable resin composition, color filter, and display device - Google Patents

Abstract

（式（１）中、Ｒ¹⁰及びＲ¹²はそれぞれ独立に炭素数１〜６のアルキル基等を表し、Ａはアニオンを表し、ｍ及びｎはそれぞれ独立に０〜２の整数であり、ｍ＋ｎは２以下である。）また、上記カラーフィルター用緑色硬化性樹脂組成物を用いて形成された着色層を備えたカラーフィルターである。さらに、上記カラーフィルターを備えた表示装置である。
【選択図】なしA red curable resin composition for a color filter capable of suppressing generation of crystals in a cured film during post-baking and sufficiently suppressing a decrease in contrast during post-baking or in a subsequent heating process, and a color filter using the same As well as a display device.
A color comprising a curable transparent resin composition containing a polyfunctional epoxy compound and an acid generator and a red pigment, wherein the acid generator is a diaryliodonium salt represented by the following formula (1). It is a red curable resin composition for filters.

(In the formula (1), R ¹⁰ and R ¹² each independently represents an alkyl group having 1 to 6 carbon atoms, A represents an anion, m and n are each independently an integer of 0 to 2, m + n Is a color filter having a colored layer formed using the green curable resin composition for color filters. Furthermore, the display device includes the color filter.
[Selection figure] None

Description

  The present invention relates to a red curable resin composition for a color filter used for manufacturing a color filter such as a liquid crystal display, a color filter using the red curable resin composition for the color filter, and a display device including the color filter. About.

  In the liquid crystal display industry in which color filters are used, the demand for high contrast is very high. Along with this, nano-level pigments have been used for color filter resists. When the pigment is thus miniaturized, light scattering when the polarizing plate is orthogonal is reduced and high contrast is obtained (see, for example, Patent Document 1).

  However, it has been found that when the size of the pigment is nano level, the fastness is lowered and the performance related to reliability such as heat resistance is lowered. For example, a red pigment (CI Pigment Red 254, hereinafter referred to as “PR254”) used in a resist for coloring in red is used as a high-intensity pigment. As a result, a decrease in contrast, which appears to be caused by crystal precipitation during baking or destabilization of the dispersion system, has come to appear remarkably.

  Here, contrast (also referred to as contrast ratio) is the ratio of the luminance on the display device (ON state / OFF state) when light must be transmitted (ON state) and when it must be blocked (OFF state). ). Therefore, in order to achieve high contrast, when the light must be transmitted (ON state), the luminance (hereinafter sometimes referred to as parallel luminance) is increased, while the light must be blocked It can be said that it is important to keep the value of luminance in the (OFF state) (hereinafter sometimes referred to as orthogonal luminance) small, that is, to prevent light from leaking into the OFF state.

JP 2003-89756 A

  In view of the above, an object of the present invention is to solve the above problems. That is, the present invention suppresses the generation of crystals in the cured film during post-baking and the subsequent heating process during the production of the color filter, and sufficiently suppresses the decrease in contrast during the post-baking and the subsequent heating process. An object of the present invention is to provide a red curable resin composition. Another object of the present invention is to provide a color filter that contains the red curable resin composition for a color filter as a material for forming a colored layer and has good heat resistance. Another object of the present invention is to provide a display device provided with the color filter.

  In order to solve the above-mentioned problems, the present inventors have examined the cause of crystal precipitation and the resulting decrease in contrast. In the red curable resin composition for color filters using a specific diaryl iodonium salt as an acid generator. When added, the generation of crystals is suppressed, and as a result, even if a heat treatment such as post-baking is performed, it has been found that there is no significant reduction in contrast thereafter and the present invention has been conceived. That is, the present invention is as follows.

（上記式（１）中、Ｒ¹⁰及びＲ¹²はそれぞれ独立に炭素数１〜６のアルキル基を表し、Ａはアニオンを表し、ｍ及びｎはそれぞれ独立に０〜２の整数であり、ｍ＋ｎは２以下である。）
［２］ 多官能エポキシ化合物が三官能以上のエポキシ化合物である［１］に記載のカラーフィルター用赤色硬化性樹脂組成物。
［３］ 前記赤色顔料の分散粒径が１５〜６０ｎｍである［１］または［２］に記載のカラーフィルター用赤色硬化性樹脂組成物。
［４］ 前記赤色顔料が２種以上の顔料で構成され、前記顔料のうち含有量の最も高い主顔料がＣ．Ｉ．ピグメントレッド２５４である［１］〜［３］のいずれかに記載のカラーフィルター用赤色硬化性樹脂組成物。
［５］ 熱硬化開始温度が９０〜１４０℃である［１］〜［４］のいずれかに記載のカラーフィルター用赤色硬化性樹脂組成物。
［６］ ［１］〜［５］のいずれかに記載のカラーフィルター用赤色硬化性樹脂組成物を用いて形成された着色層を備えたカラーフィルター。
［７］ ［６］に記載のカラーフィルターを備えた表示装置。 [1] A color comprising a curable transparent resin composition containing a polyfunctional epoxy compound and an acid generator and a red pigment, wherein the acid generator is a diaryliodonium salt represented by the following formula (1) Red curable resin composition for filters.

(In the above formula (1), R ¹⁰ and R ¹² each independently represents an alkyl group having 1 to 6 carbon atoms, A represents an anion, m and n are each independently an integer of 0 to 2, m + n Is 2 or less.)
[2] The red curable resin composition for a color filter according to [1], wherein the polyfunctional epoxy compound is a trifunctional or higher functional epoxy compound.
[3] The red curable resin composition for a color filter according to [1] or [2], wherein the dispersed particle diameter of the red pigment is 15 to 60 nm.
[4] The red pigment is composed of two or more pigments, and the main pigment having the highest content among the pigments is C.I. I. The red curable resin composition for a color filter according to any one of [1] to [3], which is CI Pigment Red 254.
[5] The red curable resin composition for a color filter according to any one of [1] to [4], wherein the thermosetting start temperature is 90 to 140 ° C.
[6] A color filter provided with a colored layer formed using the red curable resin composition for a color filter according to any one of [1] to [5].
[7] A display device comprising the color filter according to [6].

According to the present invention, it is possible to provide a red curable resin composition for a color filter that can suppress generation of crystals in a cured film during post-baking and can sufficiently suppress a decrease in contrast during post-baking or in a subsequent heating step. Can do. Moreover, the color filter which has the favorable heat resistance can be provided by including the said red curable resin composition for color filters as a formation material of a colored layer. Furthermore, a display device including the color filter can be provided.

[Red curable resin composition]
The red curable resin composition of the present invention comprises a curable transparent resin composition containing a polyfunctional epoxy compound and an acid generator, and a red pigment, and is blended with other optional additives.

<Curable transparent resin composition containing polyfunctional epoxy compound and acid generator>
The curable transparent resin composition according to the present invention includes a polyfunctional epoxy compound and an acid generator as essential components, and is applied onto a substrate from the viewpoint of imparting sufficient strength, durability, and adhesion to the coating film. In addition, it is preferable to use a curable transparent resin composition that can be further polymerized and cured by heat during post-baking after forming a pattern by mask exposure, development, or the like. Examples of such a curable transparent resin composition include a photosensitive transparent resin composition that can change the solubility of an exposed portion by light such as ultraviolet rays.

  The photosensitive transparent resin composition includes a photopolymerization initiator that can be decomposed by exposure to generate radicals, acids, and bases, and a polyfunctional monomer that is polymerized by the generated radicals, acids, and bases. Examples include a negative photosensitive transparent resin composition in which a coating film pattern of only the exposed portion can be prepared by curing the portion and dissolving and removing the unexposed portion.

  In the red curable resin composition, the curable transparent resin composition is preferably a negative photosensitive transparent resin composition from the viewpoint that a very strong cured film can be formed. In the present invention, the negative photosensitive transparent resin composition that can be polymerized and cured by light such as ultraviolet rays is, for example, (i) a polyfunctional epoxy compound, (ii) an acid generator, (iii) a binder resin, (iv) It is composed of a polyfunctional (meth) acrylic monomer, (v) a photopolymerization initiator, and the like.

(I) Polyfunctional epoxy compound As the polyfunctional epoxy compound, it is preferable to use a trifunctional or higher polyfunctional epoxy compound. Examples thereof include epoxy compounds such as bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, aliphatic epoxy compounds, or bisphenol fluorene type epoxy compounds. .

  Specific examples include low molecular weight epoxy compounds such as sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, and trimethylolpropane polyglycidyl ether. Examples of product names include EX-611, EX-421, EX-512, EX-521, EX-611, EX-614, EX-622, EX-314, EX-321, and EX-411 manufactured by Nagase ChemteX. It is done.

Moreover, you may replace a part or all of a polyfunctional epoxy compound with a polyfunctional oxetane compound. The oxetane compound is, for example, an oxetane such as a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, an aliphatic epoxy compound, or a bisphenol fluorene type epoxy compound. Compounds and the like.
In addition, a polymer type epoxy compound such as poly (meth) acrylate containing an epoxy novolac resin or glycidyl (meth) acrylate as a polymerization component can also be used.
These may be used singly or in combination of two or more.

  It is preferable to mix | blend 1-50 mass% of polyfunctional epoxy compounds with respect to solid content of curable transparent resin composition, and it is more preferable to set it as 1-30 mass%. By setting the content to 1 to 30% by mass, curing sufficient to improve the heat resistance during baking at the time of manufacturing the color filter can be performed without reducing the storage stability of the red curable resin composition. The term “solid content” as used herein means the weight obtained by removing the volatile solvent from each resin composition.

(Ii) Acid generator The acid generator according to the present invention is a diaryliodonium salt represented by the following formula (1).

（上記式（１）中、Ｒ¹⁰及びＲ¹²はそれぞれ独立に炭素数１〜６のアルキル基を表し、Ａはアニオンを表し、ｍ及びｎはそれぞれ独立に０〜２の整数であり、ｍ＋ｎは２以下である。）

(In the above formula (1), R ¹⁰ and R ¹² each independently represents an alkyl group having 1 to 6 carbon atoms, A represents an anion, m and n are each independently an integer of 0 to 2, m + n Is 2 or less.)

The acid generator is preferable because it generates both free radicals and acids by light and can improve the curability during both exposure and baking. Further, by making R ¹⁰ and R ¹² an alkyl group having 1 to 6 carbon atoms, the radical diffusion rate is improved, the curability of the film is improved during exposure, that is, before post-baking, and acid is also generated at the same time. In addition, it is considered that the epoxy compound is efficiently polymerized at the time of post-baking to improve the curability at the initial stage of post-baking, to suppress crystal precipitation due to pigments and the like, and to suppress subsequent reduction in contrast.

The alkyl group having 1 to 6 carbon atoms may be any of linear, branched, and cyclic (cycloalkyl group). Among them, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, 2- A butyl group and an isobutyl group are preferable. Examples of the anion represented by A include hexafluorophosphoric acid (PF ₆ ⁻ ), tetrafluoroboric acid (BF ₄ ⁻ ), hexafluoroantimonic acid (SbF ₆ ⁻ ), hexafluoroarsenic acid (AsF ₆ ⁻ ). Anions that generate strong acids such as tetrakis (pentafluorophenyl) boric acid and sulfonic acid derivatives, and strong acids such as hexafluorophosphoric acid (PF ₆ ⁻ ) tetrakis (pentafluorophenyl) boric acid and trifluoromethanesulfonic acid. The anion to be generated is preferred.

  Examples of the iodonium salt represented by the above formula (1) include the following.

  It is preferable to mix | blend the iodonium salt which concerns on this invention so that it may become 0.5-20 mass% with respect to the polyfunctional epoxy compound used, and it is more preferable to mix | blend so that it may become 0.5-10 mass%. preferable. A polyfunctional epoxy compound can be fully hardened, suppressing the influence by coloring by an iodonium salt by setting it as 0.5-20 mass%.

(Iii) Binder resin The binder resin preferably has high compatibility with other components, and when a pattern is formed by alkali development, it is preferable to use a resin having a carboxyl group in the side chain.

  Preferred binder resins include (meth) acrylic copolymers, epoxy (meth) acrylate resins, and the like. Those having a polymerizable functional group such as an ethylenically unsaturated group in the side chain are preferred. It is because the film strength of the cured film formed improves by containing a polymerizable functional group. These acrylic copolymers and epoxy acrylate resins may be used in combination of two or more.

  The (meth) acrylic copolymer is obtained by copolymerizing an ethylenically unsaturated monomer and another ethylenically unsaturated monomer. The (meth) acrylic copolymer may further contain a structural unit having an aromatic carbocyclic ring or an alicyclic structure. The aromatic carbocycle functions as a component that imparts coating properties to the curable resin composition, and the alicyclic structure functions as a component that imparts transparency and heat resistance of the cured film.

  The (meth) acrylic copolymer may further contain a structural unit having an ester group. By using a structural unit having an ester group, a component that controls compatibility with various polymerizable functional groups and other components can be introduced into the side chain via the ester bond.

  Moreover, as said (meth) acrylic-type copolymer containing a polymeric functional group, with respect to the one part carboxyl group of the said acrylic-type copolymer, glycidyl (meth) acrylate, 3, 4- epoxy cyclohexylmethyl ( Epoxy groups and oxetanyl groups of compounds having an epoxy group, an oxetanyl group and an ethylenically unsaturated group in one molecule such as (meth) acrylate, 4- (2,3-epoxypropyl) butyl (meth) acrylate, and allyl glycidyl ether. Or reacting an isocyanate group of a compound having an isocyanate group and an ethylenically unsaturated group in one molecule, such as 2-methacryloyloxyethyl isocyanate, with respect to some or all of the hydroxyl groups of the acrylic copolymer Acrylic copolymer having an ethylenically unsaturated group in the side chain Coalescence can also be used.

When the pattern is formed by alkali development, the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the (meth) acrylic copolymer is preferably 5 to 50% by mass, and 10 to 40% by mass. More preferably.
When the copolymerization ratio is 5% by mass or more, a decrease in the solubility of the obtained coating film in an alkaline developer can be prevented, and pattern formation can be facilitated. Further, when the copolymerization ratio is 50% by mass or less, it is possible to prevent the formed pattern from falling off from the substrate and the film roughness of the pattern surface during development with an alkaline developer.

  The molecular weight of the acrylic copolymer is preferably 1,000 to 500,000, and more preferably 3,000 to 200,000. When it is 1,000 or more, it is possible to prevent the binder function after curing from being significantly lowered, and the viscosity of the curable resin composition itself can be within an appropriate range. In particular, when the pattern is formed by alkali development, when the pattern is 500,000 or less, pattern formation can be facilitated during development with an alkali developer.

  The epoxy (meth) acrylate resin is not particularly limited, but an epoxy (meth) acrylate compound obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride is suitable. ing.

The epoxy compound is not particularly limited as long as it does not inhibit the compatibility with other components. For example, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, phenol novolac type An epoxy compound such as an epoxy compound, a cresol novolac type epoxy compound, an aliphatic epoxy compound, or a bisphenol fluorene type epoxy compound can be given.
Examples of the oxetane compound include oxetane compounds in which the epoxy group of the above-described epoxy compound is substituted with an oxetanyl group. These may be used alone or in combination of two or more.

  Examples of the unsaturated group-containing monocarboxylic acid include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, and (meth) acryloyloxyethyl hexahydrophthalic acid. (Meth) acrylic acid dimer, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid and the like. Also, half-ester compounds that are reaction products of hydroxyl group-containing acrylates with saturated or unsaturated dibasic acid anhydrides, reaction products of unsaturated group-containing monoglycidyl ethers with saturated or unsaturated dibasic acid anhydrides. A half ester compound is also mentioned. These unsaturated group-containing monocarboxylic acids may be used alone or in combination of two or more.

  Examples of the acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, anhydrous Dibasic acid anhydrides such as methylendomethylenetetrahydrophthalic acid, chlorendic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride Aromatic polycarboxylic anhydrides such as biphenyl ether tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, endobicyclo- [2,2,1] -hept-5-ene-2, - polycarboxylic anhydride derivatives such as dicarboxylic acid anhydrides, and the like. These may be used alone or in combination of two or more.

  The molecular weight of the epoxy (meth) acrylate compound having a carboxyl group thus obtained is preferably 1000 to 40000, and more preferably 2000 to 5000.

  It is preferable to mix | blend 10-70 mass% with respect to solid content of a curable transparent resin composition, and, as for binder resin, it is more preferable to set it as 20-50 mass%. By setting it as 10-70 mass%, film formability and alkali developability can be provided to a green curable resin composition, without inhibiting hardening of another component.

(Iv) Polyfunctional (meth) acrylic monomer Examples of polyfunctional (meth) acrylic monomers include di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol; polyalkylene glycols such as polyethylene glycol and polypropylene glycol Di (meth) acrylates; poly (meth) acrylates of polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. and their dicarboxylic acid modified products; polyesters, epoxy resins, urethane resins Oligo (meth) acrylates such as alkyd resin, silicone resin, and spirane resin; both-end hydroxypoly-1,3-butadiene, both-end hydroxypolyisoprene, both-end hydroxypolycaprola Di (meth) acrylates of both ends hydroxylated polymers such as tons; can be mentioned tris (2- (meth) acryloyloxyethyl) phosphate and the like.

  Of these polyfunctional (meth) acrylic monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid-modified products are preferred, specifically, trimethylolpropane tri (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate modified with succinic acid, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable. A polyfunctional (meth) acryl monomer can be used individually or in mixture of 2 or more types.

  The amount of the polyfunctional (meth) acrylic monomer used is preferably 5 to 500 parts by mass and more preferably 20 to 300 parts by mass with respect to 100 parts by mass of the binder resin. By making the usage-amount of a polyfunctional monomer into 5 mass parts or more, it can prevent that film | membrane intensity | strength and the smoothness of the film | membrane surface fall. Moreover, it can prevent that a red curable resin composition falls below the suitable viscosity which can be apply | coated by desired thickness by setting it as 500 mass parts or less.

  A part of the polyfunctional (meth) acrylic monomer can be replaced with a monofunctional (meth) acrylic monomer. Examples of such monofunctional monomers include carboxyl group-containing unsaturated monomers or other unsaturated monomers constituting alkali-soluble resins, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate. Etc. Among these monofunctional (meth) acrylic monomers, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone mono Preferred are methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, and the like. A monofunctional monomer can be used individually or in mixture of 2 or more types. The use ratio of the monofunctional monomer is preferably 90% by mass or less and more preferably 50% by mass or less with respect to the total amount of the polyfunctional (meth) acrylic monomer and the monofunctional (meth) acrylic monomer. preferable.

  Furthermore, a hardening accelerator can be used. Specific examples of the curing accelerator include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-4,6-dimethyl. Examples include aminopyridine, 1-phenyl-5-mercapto-1H-tetrazole, and 3-mercapto-4-methyl-4H-1,2,4-triazole.

(V) Photopolymerization initiator The photopolymerization initiator may be unnecessary because the above-mentioned acid generator generates both an acid and a radical, but it generates an acid for high sensitivity during patterning. It is preferable to use an agent and a photopolymerization initiator in combination.

  As the photopolymerization initiator, a radical polymerization initiator can be used, for example, a compound that generates free radicals by the energy of ultraviolet rays, and a benzophenone derivative such as benzoin or benzophenone or a derivative thereof such as an oxime ester; Derivatives; xanthone and thioxanthone derivatives; halogen-containing compounds such as chlorosulfonyl, chloromethyl polynuclear aromatic compounds, chloromethyl heterocyclic compounds, chloromethylbenzophenones; triazines; fluorenones; haloalkanes; photoreductive dyes and reducing agents And redox couples; organic sulfur compounds; peroxides and the like. Preferred examples include ketone-based and biimidazole-based compounds. Specifically, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 907, OXE-01, OXE-02 (above, manufactured by Ciba Specialty Chemicals) ), Darocur (Merck), Adeka 1717 (Asahi Denka Kogyo), 2,2′-bis (o-chlorophenyl) -4,5,4′-tetraphenyl-1,2′-biimidazole (Kurokin Kasei) And other commercial products. Other photopolymerization initiators can be used alone or in combination of two or more. When an initiator that does not absorb at the exposure wavelength is used, it is necessary to use a compound that absorbs at the exposure wavelength as a sensitizer.

  It is preferable to mix | blend 1-40 mass% with respect to a photopolymerizable monomer, and, as for a photoinitiator, it is more preferable to set it as 1-20 mass%. By setting the content to 1 to 40% by mass, it is possible to perform curing at a level capable of patterning with sufficient sensitivity during photocuring.

<Red pigment>
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276, etc., but any red pigment can be used without limitation. In addition, if the pigment has low heat resistance and deteriorates and crystallizes during post-baking, the effect of suppressing the decrease in contrast is more easily obtained.
Examples of red pigments include C.I. I. Pigment Red 254 is preferably used. When the red pigment is composed of two or more pigments, the main pigment having the highest content is C.I. I. Pigment Red 254 is preferable in terms of luminance and color reproduction range. Here, the main pigment is a pigment including the most part by mass with respect to the total mass of the coloring pigments contained in the colored resin composition.
The primary particle size of the red pigment preferably has a distribution in the range of 5 to 100 nm, and the average dispersed particle size of the dispersed red pigment particles is preferably 15 to 60 nm.

  In addition, as long as the desired chromaticity can be achieved, another pigment (an orange pigment or a yellow pigment) may be further contained. The other pigment is preferably 3 to 45% by mass, more preferably 3 to 40% by mass in the total pigment (red pigment + other pigment).

The red pigment is preferably blended in an amount of 25 to 80 mass%, more preferably 35 to 80 mass%, based on the total solid content of the red curable resin composition. When the red pigment is 25% by mass or more, the color density when the curable resin composition is applied to a predetermined film thickness (usually 1.0 to 4.0 μm) can be made sufficient, and 35 When it is at least mass%, a film thickness of 3 μm or less can be achieved. Moreover, the quantity with respect to the whole solid content of curable resin composition shall be sufficient by setting it as 80 mass% or less, and it becomes easy to acquire the effect of the heat resistance improvement by hardening.
Here, in the present specification, the solid content for specifying the blending ratio includes all components except the solvent, and liquid polymerizable monomers and the like are also included in the solid content.

  In the red curable resin composition, the mass ratio (P / V) of the entire pigment (P) and the solid content (V) other than the pigment is preferably 0.3 to 0.8, 0.4 More preferably, it is -0.8.

  The various pigments used are, for example, a method of mechanically pulverizing various pigment particles as typified by the solvent salt milling method; the various pigment particles are once returned to the molecular state by dissolution, etc., and the temperature changes And a method of precipitating in a fine particle state using a poor solvent or the like; a method of directly producing fine particle pigments during synthesis of various pigments by controlling reaction conditions, and the like.

<Pigment dispersant>
A pigment dispersant is usually used for pigments such as red pigments. The pigment dispersant is blended in order to disperse the various pigments satisfactorily. Examples of the pigment dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants, and block polymer and graft polymer type polymer dispersants. Among the surfactants, polymer dispersants as exemplified below are preferable.

  In addition, a pigment derivative in which a red pigment or an aromatic compound having a similar skeleton is combined with a solvent affinity such as an alkyl chain, a polyether chain, a polyester chain, a sulfonic acid group, or a sulfonamide group, or a site having an acid-base adsorption effect May be used as a pigment dispersant.

  As pigment dispersants, (co) polymers of unsaturated carboxylic esters such as poly (meth) acrylic acid esters; (parts) of (co) polymers of unsaturated carboxylic acids such as poly (meth) acrylic acid Amine salts, (partial) ammonium salts and (partial) alkylamine salts; hydroxyl group-containing unsaturated carboxylic acid ester (co) polymers such as poly (meth) acrylic acid esters and their modified products; polyurethanes; Saturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; amides obtained from the reaction of poly (lower alkylene imines) with free carboxyl group-containing polyesters and their salts are non-aqueous (solvent type) It is preferable because it is a dispersant that can utilize steric hindrance and acid-base adsorption effective for the dispersion of the above.

Among them, among (co) polymers of unsaturated carboxylic acid esters such as poly (meth) acrylic acid esters, dimethylaminoethyl (meth) acrylate or quaternary ammonium salts of dimethylaminoethyl (meth) acrylate Polymers containing repeating units derived from are preferred.
Examples of the polymer include methyl (meth) acrylate, n-butyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and γ-butyrolactone modified product of (meth) acrylic acid. Copolymers with other (meth) acrylic acid esters are preferably used. Among them, a copolymer containing a repeating unit derived from a quaternary ammonium salt of methyl (meth) acrylate and dimethylaminoethyl (meth) acrylate or dimethylaminoethyl (meth) acrylate is preferably used. A block copolymer containing methyl poly (meth) acrylate and dimethylaminoethyl polyblock (meth) acrylate or a quaternary ammonium salt thereof is preferably used.
Further, a block copolymer obtained by reacting a tertiary amine with a phosphate ester, a sulfonate ester, or a borate ester to form a quaternary ammonium is more preferably used.

  In the present specification, (meth) acryl means either acryl or methacryl, (meth) acrylate means either acrylate or methacrylate, and (meth) acryloyl. Means either acryloyl or methacryloyl.

  Moreover, as a pigment dispersant, a polyallylamine derivative is preferable. The polyallylamine derivative suitably used includes, for example, three kinds of compounds such as a polyester having a side chain of polyallylamine and a polyester having a free carboxyl group, polyamide, or a co-condensate of ester and amide (polyesteramide). A polyallylamine derivative represented by the following general formula (I) is exemplified by reaction with one or more compounds selected from:

（式中、Ｘ及びＹは、それぞれ独立に水素、重合開始剤残基、及び連鎖移動触媒残基のいずれかを、Ｒ¹は遊離のアミノ基、下記一般式（II）、又は（III）で示される基を、ｎは２〜１，０００の整数を表す。但しｎ個のＲ¹中、少なくとも１個は一般式（III）で示される基を表す。

(Wherein X and Y are independently hydrogen, a polymerization initiator residue, or a chain transfer catalyst residue, R ¹ is a free amino group, the following general formula (II), or (III): N represents an integer of 2 to 1,000, provided that at least one of n R ^{1 s} represents a group represented by formula (III).

（式中、Ｒ²は遊離のカルボン酸を有するポリエステル、遊離のカルボン酸を有するポリアミド、及び遊離のカルボン酸を有するポリエステルアミドのいずれかからカルボキシル基を除いた残基を表す。）

(In the formula, R ² represents a residue obtained by removing a carboxyl group from any of a polyester having a free carboxylic acid, a polyamide having a free carboxylic acid, and a polyester amide having a free carboxylic acid.)

  This polyallylamine derivative includes, for example, a polyallylamine having a polymerization degree of 2 to 1,000, a polyester having a free carboxyl group, the following general formula (IV) or (V), and the following general formula (VI) or One kind of polyamide represented by (VII) can be produced as a raw material alone or in combination of two or more kinds.

（式中Ｒ³は、炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基を、そしてａは２〜１００の整数を示す。）

(In the formula, R ³ represents a linear or branched alkylene group having 2 to 20 carbon atoms, and a represents an integer of 2 to 100.)

（式中Ｒ⁴は、炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基、Ｃ₆Ｈ₄またはＣＨ＝ＣＨを、Ｒ⁵は炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基、ポリアルキレングリコールから２つの水酸基を除いた残基を、そしてｂは２〜１００の整数を示す。また、前記鎖中にエーテル結合を有することもある。）

Wherein R ⁴ is a linear or branched alkylene group having 2 to 20 carbon atoms, C ₆ H ₄ or CH═CH, and R ⁵ is a linear or branched alkylene having 2 to 20 carbon atoms. A group, a residue obtained by removing two hydroxyl groups from polyalkylene glycol, and b represents an integer of 2 to 100. The chain may also have an ether bond.)

（式中Ｒ⁶は、炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基を、そしてｃは２〜１００の整数を示す。）

(In the formula, R ⁶ represents a linear or branched alkylene group having 2 to 20 carbon atoms, and c represents an integer of 2 to 100.)

（式中Ｒ⁴は、炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基、Ｃ₆Ｈ₄またはＣＨ＝ＣＨを、Ｒ⁷は炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基を、そしてｄは２〜１００の整数を示す。）

(Wherein R ⁴ is a linear or branched alkylene group having 2 to 20 carbon atoms, C ₆ H ₄ or CH═CH, and R ⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms. A group, and d represents an integer of 2 to 100.)

  The polyallylamine derivative suitably used as a pigment dispersant in the present invention is a polyester in which repeating components of general formula (IV) and general formula (V) are randomly polymerized on polyallylamine, general formula (VI) and general A polyamide in which the repeating component of formula (VII) is randomly polymerized, and further a polyesteramide in which the repeating components of general formula (IV) and / or (V) and general formula (VI) and / or (VII) are randomly polymerized It can also be produced by reacting. Moreover, what formed the salt part of the amine part of a polyallylamine derivative, phosphate ester, sulfonate ester, and borate ester is used more suitably.

  Examples of commercially available pigment dispersants include Disperbyk-101, -116, -130, -140, -160, -161, -162, -163, -164, -164, -166, and- 167, same-168, same-170, same-171, same-174, same-182, same-2000, same-2001, same--2050 (above, manufactured by Big Chemie Japan Co., Ltd.); EFKA-4046, same -4047 (above, manufactured by EFAK CHEMICALS); Solsperse 12000, 13240, 13940, 17000, 20000, 24000GR, 24000SC, 27000, 28000, 32000, 33500, 33500, 35200, 37500 (above, manufactured by Nippon Lubrizol Co., Ltd.); Azisper PB711, 21, the 822,823,824 (manufactured by Ajinomoto Fine-Techno Co.); and the like. Moreover, it is more preferable to use what refine | purified them in order to improve the reliability of a color filter.

  The blending amount of the pigment dispersant is preferably 20 to 80 parts by mass and more preferably 20 to 60 parts by mass with respect to 100 parts by mass of the total pigment.

<Solvent>
The solvent is used for preparing a pigment dispersion in which various pigments are dispersed. For example, a red pigment dispersion in which a red pigment is dispersed can be used when a red curable resin composition is produced.

  Examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; carbitols such as methoxyethoxyethanol and ethoxyethoxyethanol. Solvent: Carbitol acetate solvents such as butyl carbitol acetate (BCA); Ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate; acetone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents: such as methoxyethyl acetate, methoxypropyl acetate, methoxybutyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate Solvent acetate solvents; Carbitol acetate solvents such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate; Ether solvents such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and propylene glycol diethyl ether; N, N-dimethylformamide Aprotic amide solvents such as N, N-dimethylacetamide and N-methylpyrrolidone; Lactone solvents such as γ-butyrolactone; Unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene; N-heptane, N -Saturated hydrocarbon solvents such as hexane and N-octane; and organic solvents such as propylene glycol monomethyl ether acetate.

  Among these solvents, ketone solvents such as cyclohexanone; cellosolve acetate solvents such as methoxyethyl acetate, ethoxyethyl acetate, and ethyl cellosolve acetate; methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA), etc. Carbitol acetate solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol diethyl ether and other ether solvents; methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate and the like; propylene glycol monomethyl ether acetate are preferred Used for.

Among them, the solvent used in the present invention is selected from the group consisting of propylene glycol monomethyl ether acetate (CH ₃ OCH ₂ CH (CH ₃ ) OCOCH ₃ ), propylene glycol monomethyl ether, butyl carbitol acetate (BCA) and cyclohexanone. It is preferable from the point of the solubility of another component, and the applicability | paintability that it is 1 or more types.

These solvents may be used alone or in combination of two or more.
The red pigment dispersion is preferably prepared so that the solvent as described above has a ratio of 60 to 85% by mass with respect to the total amount of the pigment dispersion containing the solvent. When the amount of the solvent is too small, the viscosity is increased, and the pigment dispersibility and the pigment dispersion stability with time are likely to be lowered. Moreover, when there are too many solvents, a pigment density | concentration falls and it may be difficult to achieve the chromaticity coordinate which makes a resin composition the target after preparation.

  If necessary, the red pigment dispersion may further contain a pigment dispersion auxiliary resin and other components. Examples of the pigment dispersion auxiliary resin include a binder resin described below.

  The average dispersed particle diameter of the pigment particles in the red pigment dispersion is preferably 15 to 60 nm, more preferably 15 to 50 nm, and still more preferably 15 to 45 nm.

  Here, the dispersed particle diameter of the pigment particles in the red pigment dispersion is a dispersed particle diameter of pigment particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. It is. For particle size measurement using a laser light scattering particle size distribution meter, the solvent used in the pigment dispersion is appropriately diluted to a concentration that can be measured with the laser light scattering particle size distribution meter (eg, 500 times). It can be measured by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrack particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average dispersed particle size here is a volume average particle size.

  The red pigment dispersion can be prepared by mixing a red pigment, a pigment dispersant, and if necessary, other components in a solvent in an arbitrary order and dispersing the mixture using a known disperser.

  When using multiple types of red pigments or when using a combination of red and other pigments, prepare a pigment dispersion for each pigment, and then mix them. A red pigment dispersion may be used, or two or more pigments may be dispersed at a time to obtain a red pigment dispersion.

  Among these, the dispersion time for each pigment varies to the dispersion state where the dispersed particle size becomes the smallest, and if the dispersion is performed beyond that time, aggregation often occurs, so that a desired average dispersed particle size can be obtained. Is preferably prepared by preparing a pigment dispersion for each pigment, and then mixing them to obtain a red pigment dispersion. In this case, if different dispersants are used for the respective pigments, they may be aggregated. Therefore, it is preferable that the types of the pigment dispersants used for dispersing each pigment are the same. However, this does not apply when the pigments are dispersed and stabilized.

  Examples of the dispersing machine for performing the dispersion treatment include roll mills such as two rolls and three rolls; ball mills such as a ball mill and a vibration ball mill; paint conditioners; bead mills such as a continuous disk type bead mill and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 to 2.00 mm, and more preferably 0.10 to 1.0 mm.

  When dispersing various pigments, it is preferable to add zirconia beads or the like as appropriate and perform dispersion for about 1 to 5 hours using a paint shaker (manufactured by Asada Steel Corporation) or the like. Specifically, it is dispersed for 1 hour with 2 mm zirconia beads having a relatively large bead diameter, and further for 2 to 10 hours with 0.1 mm zirconia beads having a relatively small bead diameter. Moreover, it is preferable to filter with a membrane filter of 0.5 to 0.1 μm after dispersion.

In this way, a red pigment dispersion is obtained. This red pigment dispersion can be used as a preliminary preparation for preparing a red curable resin composition having excellent pigment dispersibility.
<Other ingredients>
The red curable resin composition for a color filter according to the present invention may further contain a surfactant, an adhesion promoter, a surface conditioner (leveling agent), or other components as necessary.

(Surfactant)
When the surfactant is used in various combinations, the dispersion stability can be improved. Examples of the surfactant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. For example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether Examples include alkylphenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; and polyethyleneimines.

  The product names of the surfactants are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFuck (Dainippon Ink Chemical Co., Ltd.) )), Florard (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), and the like.

(Adhesion promoter)
Examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.

(Leveling agent)
Examples thereof include commercially available silicon-based, polyoxyalkylene-based, fatty acid ester-based, and special acrylic polymers.

  A red curable resin composition is prepared by adding a red pigment and a curable transparent resin composition together with other compounding components as necessary, into a solvent (single solvent or mixed solvent), and mixing them by a known dispersion method. Can be produced by dissolving or dispersing the.

  However, in the above method, a large amount of red pigment cannot be sufficiently dispersed in the solvent, and the desired pigment dispersed particle size distribution may not be obtained. Therefore, a pigment dispersion as described above is prepared in advance, while a curable transparent resin composition in which other components such as a binder resin are mixed, dispersed, or dissolved with a solvent is prepared. Then, by mixing these red pigment dispersion and the curable transparent resin composition and performing a dispersion treatment as necessary, the effects of the present invention are achieved, and the pigment dispersibility and the pigment dispersion stability over time are excellent. A red curable resin composition for a color filter can be easily obtained.

[Curing start temperature of red curable resin composition]
By setting the curing start temperature of the red curable composition to 90 ° C. to 150 ° C., it is possible to improve the curability at the time of the post-baking initial temperature rise. Further, when the curing start temperature is 90 ° C. or higher, it is possible to prevent curing during pre-baking and development cannot be performed, and it is possible to prevent a decrease in storage stability. Further, when the curing start temperature is 150 ° C. or lower, it is possible to prevent the thermal curing rate during post-baking from being slowed, and thus it is possible to suppress pigment crystal precipitation and contrast reduction. The curing start temperature is more preferably 100 to 140 ° C.

  The curing start temperature of the red curable resin composition for a color filter of the present invention will be described in detail below. The red curable resin composition is dropped on the measurement part of the rheometer, and the volatile matter is dried at 80 ° C. for 15 minutes. Then, the viscoelasticity measurement is performed between 60 and 180 ° C., and the loss elastic modulus is the storage elasticity. The temperature at the point where the rate value was exceeded was taken as the curing start temperature. The loss elastic modulus and the storage elastic modulus were measured under the conditions of 1 Hz and 60 to 180 ° C. using a disposable cone using an rheometer MCR301 (Nihon Sieber Hegner) manufactured by Anton Paar.

[Color filter and manufacturing method thereof]
The production process of the color filter of the present invention will be described by taking as an example the case where a negative photosensitive transparent resin composition is used as the curable transparent resin composition used in the red curable resin composition. First, a red curable resin composition is applied to a support to form a coating film, dried, and then the coating film is irradiated with light such as ultraviolet rays in a predetermined pattern using a photomask. The solubility is changed between the exposed part and the unexposed part, such as selectively curing a part. Then, the cured film of a predetermined pattern is obtained by developing with an alkaline solution.

  The cured film for a color filter formed using the red curable resin composition of the present invention is post-baked to become a colored layer.

  In addition, the ratio of the luminance that is transmitted when the cured film of the red curable resin composition is sandwiched between two polarizing plates that are orthogonal or parallel to each other (the luminance when the polarizing plates are parallel / the luminance when the polarizing plates are orthogonal) (Luminance) is simply referred to as “contrast” in the present invention.

  FIG. 1 is a cross-sectional view showing an example (color filter 103) of a color filter according to the present invention. The color filter 103 covers the light shielding layer 6 formed in a predetermined pattern on the transparent substrate 5, the colored layer 7 (7R, 7G, 7B) formed in a predetermined pattern on the light shielding layer 6, and the colored layer 7. And a protective film 8 formed as described above. A transparent electrode 9 for driving liquid crystal may be formed on the protective film 8 as necessary. An alignment film 10 is formed on the innermost surface of the color filter 103, in this case, on the transparent electrode 9. Of the colored layers 7, at least the red colored layer 7R is formed through the above-described coating formation process, ultraviolet exposure, development, and post-baking process.

  The columnar spacer 12 has a shape of a convex spacer, and is formed at a plurality of predetermined positions on the transparent electrode 9 in accordance with a region (non-display region) where the light shielding layer 6 is formed. The columnar spacer 12 is formed on the transparent electrode 9, the colored layer 7, or the protective film 8. In the color filter 103, columnar spacers are formed in a sea island shape on the protective film 8 via the transparent electrode 9, but the protective film 8 and the columnar spacer 12 are integrally formed and transparent so as to cover it. An electrode layer may be formed.

  As the transparent substrate 5 of the color filter 103, a non-flexible transparent rigid material such as quartz glass, Pyrex (registered trademark) glass, synthetic quartz plate, or a flexible resin material such as a transparent resin film or an optical resin plate. The transparent flexible material which has can be used. Among them, Corning 1737 glass is a material having a small coefficient of thermal expansion, excellent in dimensional stability and workability in high-temperature heat treatment, and is an alkali-free glass containing no alkali component in the glass. Suitable for filters.

  The light shielding layer 6 is provided so as to surround between the colored layers 7R, 7G, and 7B and the outside of the colored layer forming region in order to improve the contrast of the display image. In the present invention, the light shielding layer 6 is preferably formed using a resin composition containing light shielding particles. For example, when the resin composition for forming a light shielding layer has alkali developability, first, the resin composition for forming a light shielding layer is applied onto the transparent substrate 5 and dried as necessary to form a photosensitive coating film. The light-shielding layer 6 can be formed by forming, exposing and developing the coating film through a photomask for the light-shielding layer, and performing heat treatment as necessary.

  On the other hand, when the light shielding layer forming resin composition is a thermosetting resin composition or has no alkali developability, the light shielding layer forming resin composition is printed on a predetermined region on the transparent substrate 5, After selectively attaching by thermal transfer or the like, the light shielding layer 6 can be formed by curing by heating or light irradiation.

  The thickness of the light shielding layer 6 varies depending on the color filter to be applied, and is about 0.5 to 2.5 μm.

  The colored layer 7 includes a red pattern, a green pattern, and a blue pattern arranged in a desired form such as a mosaic type, a stripe type, a triangle type, and a four colored layer arrangement type, thereby forming a display region. In the present invention, the colored layer 7 is preferably formed using a radiation-sensitive resin composition because fine patterning is possible, and this case will be described below as an example.

  First, curable resin compositions for red, green and blue are prepared. Next, a certain color, for example, the red curable resin composition of the present invention is applied on the transparent substrate 5 by a known method such as spin coating so as to cover the light shielding layer 6 to form a radiation sensitive red resin layer. Then, exposure with an electron beam is performed through an electron beam mask for red pattern, and after alkali development, the red colored layer 7R is formed by heat curing in a clean oven or the like. Thereafter, green and blue curable resin compositions are sequentially used to pattern each color in the same manner to form a green colored layer 7G and a blue colored layer 7B. The thickness of the colored layer is usually about 0.5 to 2.5 μm.

  Further, depending on the manufacturing process, after a red curable resin composition in a certain color, for example, red pattern formation, is selectively attached to a predetermined region on the transparent substrate 5 by printing, thermal transfer, ink jet, or the like, light or electron The colored layer 7G can also be formed by irradiating and curing a line.

  The protective film 8 is provided to flatten the surface of the color filter and prevent the components contained in the colored layer 7 from eluting into the liquid crystal layer. The protective film 8 covers the light-shielding layer 6 and the colored layer 7 with a known negative photocurable transparent resin composition or thermosetting transparent resin composition by a method such as spin coater, roll coater, spraying, printing, or the like. And can be formed by curing with light or heat. The thickness in the case of forming a protective film is set in consideration of the light transmittance of the resin composition, the surface state of the color filter, and the like, for example, about 0.1 to 2.0 μm. When using a spin coater, the number of revolutions is set within a range of 500 to 1500 revolutions / minute.

  The transparent electrode film 9 on the protective film 8 is made of indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), etc., and alloys thereof, sputtering method, vacuum deposition method, CVD method, etc. These are formed by a general method, and are formed into a predetermined pattern by etching using a photoresist or using a jig as necessary. The thickness of the transparent electrode is preferably about 20 to 500 nm, and more preferably about 100 to 300 nm.

  A plurality of convex spacers are provided in a non-display area on the substrate in order to maintain a cell gap when the color filter 103 is bonded to a liquid crystal driving side substrate such as a TFT array substrate. The shape and size of the convex spacer are not particularly limited as long as it can be selectively provided in a non-display region on the substrate and can maintain a predetermined cell gap over the entire substrate.

  When the columnar spacer 12 as shown in the figure is formed as the convex spacer, it has a certain height in the range of about 2 to 10 μm, and the protruding height (pattern thickness) is required for the liquid crystal layer. It can set suitably from thickness etc. Moreover, the thickness of the columnar spacer 12 can be appropriately set within a range of about 5 to 20 μm. Further, the formation density (density) of the columnar spacers 12 can be appropriately set in consideration of the thickness unevenness of the liquid crystal layer, the aperture ratio, the shape and material of the columnar spacers, for example, red, green and blue Necessary and sufficient spacer function is expressed at a ratio of one for each colored layer. The shape of such a columnar spacer may be a columnar shape, and may be, for example, a columnar shape, a prismatic shape, a truncated cone shape, or the like.

  The convex spacer can be formed using a curable resin composition. That is, first, the coating liquid of the curable resin composition is applied directly on a transparent substrate by a method such as spin coater, roll coater, spray, printing, or through another layer such as a transparent electrode, and then dried. Then, a photocurable resin layer is formed. The rotational speed of the spin coater may be set within a range of 500 to 1500 revolutions / minute, as in the case of forming the protective film. Next, this resin layer is exposed through a photomask for convex spacers and developed with a developer such as an alkaline solution to form a predetermined convex pattern, and this convex pattern is cleaned as necessary. A convex spacer is formed by heat treatment (post-baking) in an oven or the like.

  The convex spacer can be provided directly on the color filter or indirectly through another layer. For example, a transparent electrode such as ITO or a protective film may be formed on the color filter, and a convex spacer may be formed thereon, or a protective film and a transparent electrode may be formed in this order on the color filter, and the transparent electrode A convex spacer may be formed on the top.

  The alignment film 10 is provided on the inner surface side of the color filter so as to cover the display portion including the colored layer 7 and the non-display portion including the light shielding layer 6 and the columnar spacer 12. The alignment film can be formed by applying a coating solution containing a resin such as a polyimide resin by a known method such as spin coating, drying, curing with heat or light as necessary, and then rubbing.

[Display device]
When the color filter (display side substrate) and the TFT array substrate (liquid crystal drive side substrate) obtained as described above are opposed to each other and the inner peripheral side edge portions of both the substrates are bonded with a sealant, the two substrates are separated by a predetermined distance. Are bonded together with the cell gap maintained. An active matrix color liquid crystal display device belonging to the liquid crystal panel can be obtained by filling the liquid crystal in the gap between the substrates and sealing the liquid crystal.

<Example 1>
<< Production Example of Pigment Dispersant Solution: Production of Quaternary Ammonium Phosphate Type Polymer Dispersant Solution >>
In a 500 mL round bottom four-necked separable flask equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer and digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and initiator dimethylketenemethyltrimethylsilylacetal 5.81 Part by mass was added through a funnel for addition, and nitrogen substitution was sufficiently performed. 0.5 parts by mass of 1 mol / L acetonitrile solution of catalyst tetrabutylammonium m-chlorobenzoate was injected using a syringe, and 100 parts by mass of the first monomer methyl methacrylate was added using an addition funnel over 60 minutes. It was dripped. The temperature was kept below 40 ° C. by cooling the reaction flask with an ice bath. After 1 hour, 33.3 parts by mass of dimethylaminoethyl methacrylate as the second monomer was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and a block copolymer A was obtained. The block copolymer A thus obtained was confirmed by GPC (gel permeation chromatography) under the conditions of N-methylpyrrolidone, 0.01 mol / L lithium bromide added / polystyrene standard. The composition ratio MMA / DMAEMA mass ratio of methyl methacrylate (MMA) and dimethylaminoethyl methacrylate (DMAEMA) is 5/3, weight average molecular weight Mw: 8120, number average molecular weight Mn: 6840, molecular weight distribution Mw / Mn Was 1.19.

  In a 100 mL round-bottom flask, 5.0 parts by mass of block copolymer A was dissolved in 26.36 parts by mass of PGMEA, and dimethacryloyloxyethyl acid phosphate (Kyoeisha Chemical Co., Ltd. “Light Ester P”) was formed as a salt-forming component. -2M ") (1.5 equivalents with respect to the DMAEMA unit of the block copolymer) and stirring at a reaction temperature of 40 ° C for 2 hours, quaternary ammonium phosphorus having a solid content of 20% by mass is obtained. An acid salt type polymer dispersant solution was prepared.

<< Preparation of red pigment dispersion >>
C. I. Pigment Red 254 red pigment (Irgaphore BK-CF manufactured by Ciba Specialty Chemicals) (hereinafter referred to as “PR254”), 10 parts by mass of the above-described quaternary ammonium phosphate type polymer dispersant solution (solid content 20%) 30 parts by mass and 60 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were added to a 200 ml mayonnaise bottle and mixed. Thereafter, 0.1 mm zirconia beads were added and dispersed for 4 hours with a paint shaker (manufactured by Asada Tekko). As a result of measuring the obtained dispersion with a laser scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso), a red pigment dispersion having a volume average particle size (Mv) of 38 nm as a dispersed particle size of PR254 was obtained. I confirmed.

<< Preparation of curable transparent resin composition >>
Multifunctional acrylate monomer (SR399E, manufactured by Sakai Chemical Co., Ltd.) 7.6 parts by mass Photopolymerization initiator: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, Ciba (Made in Japan) 1.8 parts by weight binder resin: methacrylic acid / methyl methacrylate copolymer (copolymerization ratio: 10/90 acid value: 70 mg KOH / g weight average molecular weight 12000)
10.6 parts by mass polyfunctional epoxy compound: pentaerythritol tetraglycidyl ether (EX-411, manufactured by Nagase ChemteX) 3.4 parts by mass acid generator: diaryl iodonium salt represented by formula (1-1) (PI2074, Rhodia) 1.8 parts by mass Solvent: PGMEA (Daicel Chemical) 25 parts by mass

  The above was mixed and stirred to obtain a photosensitive transparent resin composition.

<< Preparation of red curable resin composition >>
Red pigment dispersion 9.2 parts by weight photosensitive transparent resin composition 5.1 parts by weight KBM-503 (manufactured by Shin-Etsu Chemical) 0.2 parts by weight Megafax R-08MH (manufactured by Dainippon Ink and Chemicals) 0.02 mass PGMEA 5.7 parts by mass

The above was mixed to prepare a red curable resin composition.
As a result of measuring the curing start temperature of the obtained red curable resin composition using a rheometer, the curing start temperature was 141 ° C.

The obtained red curable resin composition was spin-coated on a glass substrate so that the chromaticity x with a C light source after drying was 0.645 and heated at 80 ° C. for 3 minutes. Thereafter, 60 mJ / cm ² of ultraviolet light was irradiated from the coating film side with a high-pressure mercury lamp and post-baked at 260 ° C. for 30 minutes to form a red colored layer for a color filter.

For the measurement of contrast, first, a contrast measuring device CT-1 manufactured by Aisaka Electric (light source: F10 lamp between cold cathodes, luminance meter: LS-100 manufactured by Konica Minolta, spectral luminance meter: CS-1000T manufactured by Konica Minolta) is used. The brightness was measured. Using this luminance measurement value, the contrast was derived by the following equation.
Contrast = parallel luminance (cd / m ² ) / orthogonal luminance (cd / m ² )

  The contrast values before and after post-baking were 2980 (before post-baking) and 2707 (after post-baking), and the contrast reduction rate was 9.2%. When observed with an Olympus optical microscope BX-51, there was no crystal precipitation on the substrate. It was found that the precipitation of crystals was reduced and the decrease in contrast was suppressed. Thereby, it turned out that the red colored layer obtained from an Example has favorable heat resistance.

<Example 2>
A red colored layer was formed on the glass substrate in the same manner as in Example 1 except that the photopolymerization initiator was not added and the mass was replaced with PI2074. And evaluation similar to Example 1 was performed. As a result of measuring the curing start temperature of the obtained red curable resin composition using a rheometer, the curing start temperature was 137 ° C.
The contrast values before and after post-baking were 2948 (before post-baking) and 2715 (after post-baking), and the contrast reduction rate was 7.9%. When observed with an Olympus optical microscope BX-51, there was no crystal precipitation on the substrate. It was found that the precipitation of crystals was reduced and the decrease in contrast was suppressed. Thereby, it turned out that the red colored layer obtained from an Example has favorable heat resistance.

<Comparative Example 1>
A red colored layer was formed on the glass substrate in the same manner as in Example 1 except that the mass was replaced with Irgacure 907 without blending the acid generator. And evaluation similar to Example 1 was performed.
As a result of measuring the curing start temperature of the obtained red curable resin composition using a rheometer, the curing start temperature was 153 ° C.
The values of contrast before and after post-baking were 2932 (before post-baking) and 327 (after post-baking), and the contrast reduction rate was 88.8%. Many crystal precipitations occurred on the substrate. This significantly reduced the contrast.

<Comparative example 2>
A red colored layer was formed on the glass substrate in the same manner as in Example 1 except that the mass was replaced with Irgacure 907 and SR399E without blending the acid generator and the polyfunctional epoxy compound. And evaluation similar to Example 1 was performed.
As a result of measuring the curing start temperature of the obtained red curable resin composition using a rheometer, the curing start temperature was 158 ° C.
The contrast values before and after post-baking were 2843 (before post-baking) and 183 (after post-baking), and the contrast reduction rate was 93.6%. Many crystal precipitations occurred on the substrate. This significantly reduced the contrast.

<Comparative Example 3>
A red curable resin composition was prepared in the same manner as in Example 1 except that BBI-105 (manufactured by Midori Chemical) represented by the following formula was used as the acid generator, and a red colored layer was formed on the glass substrate. Formed.

  When the same evaluation as in Example 1 was performed, the contrast values before and after post-baking were 2742 (before post-baking) and 1328 (after post-baking), and the contrast reduction rate was 51.6%. Many crystal precipitations occurred on the substrate. This significantly reduced the contrast. The curing start temperature of this red curable resin composition was 172 ° C.

It is sectional drawing which shows an example of the color filter of this invention typically.

Explanation of symbols

DESCRIPTION OF SYMBOLS 5 Transparent substrate 6 Light-shielding layer 7 (7R, 7G, 7B) Colored layer 8 Protective film 9 Transparent electrode 10 Orientation film 12 Columnar spacer 103 Color filter

Claims (7)

Red for color filters, comprising a curable transparent resin composition containing a polyfunctional epoxy compound and an acid generator and a red pigment, wherein the acid generator is a diaryliodonium salt represented by the following formula (1). Curable resin composition.

(In the above formula (1), R ¹⁰ and R ¹² each independently represents an alkyl group having 1 to 6 carbon atoms, A represents an anion, m and n are each independently an integer of 0 to 2, m + n Is 2 or less.)   The red curable resin composition for a color filter according to claim 1, wherein the polyfunctional epoxy compound is a trifunctional or higher functional epoxy compound.   The red curable resin composition for a color filter according to claim 1 or 2, wherein the red pigment has an average dispersed particle diameter of 15 to 60 nm.   The red pigment is composed of two or more pigments, and the main pigment having the highest content among the pigments is C.I. I. The red curable resin composition for a color filter according to any one of claims 1 to 3, which is CI Pigment Red 254.   The red curable resin composition for a color filter according to any one of claims 1 to 4, wherein the thermosetting start temperature is 90 to 150 ° C.   The color filter provided with the colored layer formed using the red curable resin composition for color filters of any one of Claims 1-5.   A display device comprising the color filter according to claim 6.

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