JP2010085767A - Green curable resin composition for color filter, color filter, and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a green curable resin composition for a color filter, the composition reducing an amount of gas generating during post-baking in the process of manufacturing a color filter and enabling a color filter having high reliability to be manufactured, and to provide a color filter and a display device using the resin composition. <P>SOLUTION: The green curable resin composition for a color filter is prepared by compounding a green pigment, a curable transparent resin composition and resin fine particles. The resin fine particles are preferably compounded in an amount of 5 to 50 parts by mass with respect to 100 parts by mass of a nonvolatile component of the curable transparent resin composition. The color filter has a color layer formed by using the above green curable resin composition for a color filter. The display device is equipped with the color filter. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a green curable resin composition for a color filter used for forming a green colored layer. The present invention also relates to a color filter and a display device using the green curable resin composition.

  Currently, large-sized thin TVs are rapidly spreading as home displays. Above all, liquid crystal TVs have been challenged to improve yield and reliability at the time of manufacture as the price and size of products have increased. In particular, since home TV is used for a long period of time, it is required to improve reliability in long-term use.

The color filter is manufactured by the following process. Forming a coating film of a photosensitive resin composition (hereinafter referred to as photosensitive coloring resin composition) in which a pigment of the first hue is dispersed on a transparent substrate, and using a mask pattern on the coating film, etc. Then, development is performed to form a first pattern of colored pixels, and the same process is repeated to form second and third hue of colored pixels. Further, an overcoat and a liquid crystal phase are overlaid from above.
At this time, after coloring pixels are patterned by a photocuring reaction, high temperature baking is performed to improve the reliability of the coating film.

  The photosensitive colored resin composition used in the production of the color filter is composed of a pigment, a pigment dispersant, a photopolymerization initiator, a monomer, and a resin that are coloring components. Here, the resin plays a role of maintaining the strength and hardness of the film and improving process suitability (see, for example, Patent Document 1).

However, when a film once formed by photocuring is baked, unreacted monomers and uncured resin are thermally decomposed and flow out as gases from the film. Such a pyrolyzate may cause foreign matters when it is recrystallized and returns to a solid state, and may cause a decrease in yield.
In addition, with the generation of this gas, the film shrinks compared to before baking. When this is remarkable, the pattern formed changes and the accuracy of the pattern deteriorates.
JP 2004-280057 A

  In view of the above, an object of the present invention is to solve the above problems. That is, the present invention provides a green curable resin composition for a color filter that can reduce the amount of gas generated during post-baking when producing a color filter and can produce a highly reliable color filter. Objective. Another object of the present invention is to provide a color filter and a display device using the green curable resin composition.

  In order to solve the above problems, the present inventors improve the hardness of the film made of the green curable resin composition by adding resin fine particles as particles other than the pigment in the green curable resin composition, As a result, the inventors have found that it is possible to suppress a decrease in thermal weight during baking when producing a color filter, and have come to the present invention.

That is, the present invention
(1) A green curable resin composition for a color filter, comprising a green pigment, a curable transparent resin composition, and resin fine particles.
(2) The green curable resin composition according to (1), wherein the resin fine particles are blended in an amount of 5 to 50 parts by mass with respect to 100 parts by mass of the nonvolatile content of the curable transparent resin composition.
(3) The green curable resin composition according to (1) or (2), wherein the resin fine particles are acrylic resin fine particles containing (meth) acrylic acid and an ester thereof as a structural unit.
(4) The green curable resin composition according to any one of (1) to (3), wherein the resin fine particles have an average particle size of 10 to 200 nm.
(5) A color filter including a colored layer formed using the green curable resin composition for a color filter according to any one of (1) to (4).
(6) A display device including the color filter according to (5).

  According to the present invention, it is possible to provide a green curable resin composition for a color filter that can reduce the amount of gas generated during post-baking when producing a color filter and can produce a highly reliable color filter. it can. Moreover, according to this invention, the color filter using the said green curable resin composition and a display apparatus can be provided.

[1. Green curable resin composition for color filter]
The green curable resin composition for color filters of the present invention (hereinafter sometimes simply referred to as “green curable resin composition”) comprises a green pigment, a curable transparent resin composition, and resin fine particles. Become. In the present invention, by adding resin fine particles to the green curable resin composition, the green curable resin composition can be hardened and a decrease in thermal weight during baking can be suppressed.

  As a patent which mix | blends particle | grains in a color filter, Unexamined-Japanese-Patent No. 10-186126 is mentioned, for example. In this publication, a material made of ceramics is used as the material of the particles. However, this has a difference in refractive index from other components in the resist, which causes light scattering and decreases the transmittance. Therefore, there is a possibility that the optical performance of the color filter is lowered. On the other hand, since the resin fine particles according to the present invention are made of resin like the resist, the difference in refractive index is not as great as the difference between the ceramic and the resist, so that light scattering can be reduced. Although not certain, unlike ceramic particles, it is close to other components that form a film, and it is considered that this effect is produced by forming a network structure together with these in the film.

  The reason why the thermal weight loss can be suppressed by blending resin fine particles is not clear, but by adding cross-linked resin fine particles, the film structure of the coating film becomes dense, the generation of decomposition products, and the generation of decomposition products It is thought that the outflow to the outside of the membrane could be suppressed.

  Hereinafter, the resin fine particles, the green pigment, the curable transparent resin composition, and other optional additives according to the present invention will be described.

<Resin fine particles>
The resin fine particles are preferably resin fine particles obtained by polymerizing a monomer having an α, β-ethylenically unsaturated group (hereinafter, monomer). Monomers used for polymerization of resin fine particles include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, and esters thereof, 2-hydroxyethyl acrylate, hydroxypropyl acrylate , 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyl group-containing monomers such as allyl alcohol and methallyl alcohol, nitrogen-containing alkyl acrylates such as dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate, or Polymerization of polymerizable amides such as methacrylate, acrylic amide, methacrylic amide, acrylonitrile, methacrylate nitrile, etc. Alkyl acrylate such as nitrile, methacrylate methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate or the like; styrene, α-methyl styrene, vinyl toluene, t-butyl styrene Polymerizable aromatic compounds such as: α-olefins such as ethylene and propylene. These monomers can be copolymerized in an arbitrary ratio of two or more in consideration of the characteristics of the fine particles to be produced. Furthermore, in addition to the above-mentioned monomers, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, succinic acid modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( It is preferable to add a polyfunctional monomer such as (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. for three-dimensional crosslinking.

  Among the above examples, acrylic resin fine particles containing (meth) acrylic acid and esters thereof as structural units are more preferable, and cross-linked acrylic resin fine particles that are three-dimensionally crosslinked as described above are more preferable.

  Of these, fine particles polymerized from the pigment dispersant used in the curable resin composition, monomers as the main components of the alkali-soluble resin, and esters thereof are more preferable. Further, those having polar groups such as amino groups and carboxyl groups in the outer shell due to the core-shell structure are preferred from the viewpoint of dispersibility in the curable resin composition.

It is preferable that 5-50 mass parts is mix | blended with respect to 100 mass parts of non volatile matters of curable transparent resin composition, and, as for resin fine particles, it is more preferable that 5-10 mass parts is mix | blended. By blending 5 to 50 parts by mass, it is possible to effectively suppress a decrease in thermal weight during post-baking.
In addition, let the mass of the non volatile matter of a curable transparent resin composition be the mass of components other than the solvent in a composition.

  The average particle size of the resin fine particles is preferably 10 to 200 nm, and more preferably 10 to 80 nm. By being 10-200 nm, the hardness of the film can be increased without impairing film optical characteristics such as permeability and luminance. The average particle size is determined by dropping a resin fine particle ultrasonically dispersed in water onto a carbon-deposited observation table and drying it, and then transmitting a transmission electron microscope TEM (JEM-200CX (acceleration voltage: 100 kV, 50,000 by JEOL)). ))), And 100 particles were arbitrarily selected and the diameter was measured.

<Green pigment>
Examples of green pigments include C.I. I. Pigment. Green. 7, C.I. I. Pigment. Green. 36, Pigment. Green. 58 and the like, but any pigment can be used without limitation.
The primary particle diameter of the green pigment preferably has a distribution in the range of 5 to 100 nm, and the average dispersed particle diameter of the dispersed green pigment particles is preferably 15 to 60 nm.

  In addition, as long as desired chromaticity can be achieved, you may further contain the other pigment (yellow pigment). The other pigment is preferably 3 to 45% by mass, more preferably 3 to 40% by mass in the total pigment (green pigment + other pigment).

The green pigment is preferably blended in an amount of 25 to 80% by mass, more preferably 35 to 80% by mass, based on the total solid content of the green curable resin composition. When the green pigment is 25% by mass or more, the transmission density when the curable resin composition is applied to a predetermined film thickness (usually 1.0 to 4.0 μm) can be made sufficient. When it is at least mass%, a film thickness of 3 μm or less can be achieved. Moreover, it becomes easy to form the pattern after hardening by setting it as 80 mass% or less.
Here, in this specification, the solid content for specifying the blending ratio includes all components except the solvent, and liquid polyfunctional monomers and the like are also included in the solid content.

  In the green curable resin composition, the mass ratio (P / V) of the whole 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>
For pigments including green pigments, pigment dispersants are usually used. 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. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable. A pigment derivative that dissolves in a small amount in a solvent may be used as a pigment dispersant.

  The pigment dispersant is appropriately selected and used in order to favorably disperse the pigment used. Specific examples include amide compounds such as nonanamide, decanamide, dodecanamide, N-dodecylhexadecanamide, N-octadecylpropioamide, N, N-dimethyldodecanamide and N, N-dihexylacetamide; diethylamine, diheptylamine, Amine compounds such as dibutylhexadecylamine, N, N, N ′, N′-tetramethylmethanamine, triethylamine, tributylamine and trioctylamine; monoethanolamine, diethanolamine, triethanolamine, N, N, N ′, N ′-(tetrahydroxyethyl) -1,2-diaminoethane, N, N, N′-tri (hydroxyethyl) -1,2-diaminoethane, N, N, N ′, N′-tetra (hydroxyethyl) Polyoxyethylene) -1,2-diamino It can be exemplified such as; Tan, 1,4-bis amines having (2-hydroxyethyl) piperazine and 1- (2-hydroxyethyl) hydroxy groups, such as piperazine. Other examples include compounds such as nipecotamide, isonipecotamide, and nicotinamide.

  Further, (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts, (partial) ammonium salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid ( Partially) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphorus Examples thereof include acid salts; amides obtained by reaction of poly (lower alkyleneimine) and free carboxyl group-containing polyesters and salts thereof.

  Examples of pigment dispersants include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid; Ammonium salts and (partial) alkylamine salts; hydroxyl group-containing unsaturated carboxylic acid ester (co) polymers such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes; Chain polyaminoamide phosphates; amides obtained by the reaction of poly (lower alkylene imines) with free carboxyl group-containing polyesters and their salts are effective for dispersion in non-aqueous systems (solvent systems) and acids It is preferable because it is a dispersant that can utilize base adsorption.

Among them, a polymer containing a repeating unit derived from dimethylaminoethyl (meth) acrylate or a quaternary ammonium salt of dimethylaminoethyl (meth) acrylate is preferable.
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.
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および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。

(In the formula, X and Y are each 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 the general 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 is, for example, a polyallylamine having a polymerization degree of 2 to 1,000, a polyester having a free carboxyl group, represented by 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.)

  In addition, 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 to polyallylamine, general formula (VI) and general A polyamide in which the repeating component of the formula (VII) is randomly polymerized, and further a polyesteramide in which the repeating components of the general formula (IV) and / or (V) and the general formula (VI) and / or (VII) are randomly polymerized. It can also be produced by reacting.

  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 green pigment dispersion in which a green pigment is dispersed can be used when producing the green curable resin composition of the present invention.

  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, etc .; propylene glycol monomethyl ether acetate is preferred Used.

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 green 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 will fall and it may be difficult to achieve the chromaticity coordinate which makes a resin composition the target after preparation.

If necessary, the green 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.
In particular, when producing a green curable resin composition using a photosensitive transparent resin composition, after confirming that the dispersibility of the pigment by the dispersant is not inhibited, a binder resin such as an alkali-soluble resin described later is used. It can be used as a dispersion auxiliary resin. In this case, various pigment particles are less likely to come into contact with each other due to the steric hindrance of the binder resin, and the effect of reducing the dispersant due to the dispersion stabilization and the dispersion stabilization effect can also be expected.

  The average dispersed particle size of the pigment particles in the green pigment dispersion is preferably 15 to 80 nm, more preferably 15 to 70 nm, and still more preferably 15 to 40 nm.

  Here, the dispersed particle diameter of the pigment particles in the green 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 at 23 ° C. 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 green pigment dispersion can be prepared by mixing a green 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 green pigments, or when using a combination of green pigments and other pigments, prepare a pigment dispersion for each pigment, and then mix them. The green pigment dispersion of the present invention may be used, or a green pigment dispersion may be obtained by dispersing two or more pigments at a time.

  In particular, the dispersion time varies up to the dispersion limit for each pigment, and the dispersion often exceeds the dispersion time. Therefore, from the viewpoint of obtaining a desired average dispersed particle size, one pigment is used. A method is preferred in which the pigment dispersions are prepared one by one and then mixed to obtain the green pigment dispersion of the present invention. 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.

  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 green pigment dispersion is obtained. This green pigment dispersion can be used as a preliminary preparation for preparing a green curable resin composition excellent in pigment dispersibility.

<Curable transparent resin composition>
In the present invention, from the point of imparting sufficient strength, durability, and adhesion to the coating film, after forming a pattern on the substrate by coating or transfer, the coating film can be cured by a polymerization reaction. A curable transparent resin composition is used. Examples of such a curable transparent resin composition include a photosensitive transparent resin composition that can be polymerized and cured by visible light, ultraviolet light, electron beam, or the like, or can be changed in solubility, or polymerized by heating. Examples include curable transparent resin compositions such as thermosetting transparent resin compositions that can be cured.

The curable transparent resin composition used in the present invention includes a photosensitive transparent resin composition, a thermosetting transparent resin composition, and both a photosensitive transparent resin composition and a thermosetting transparent resin composition. What is included can be used.
It is preferable to mix | blend 15-95 mass% of curable transparent resin compositions with respect to the solid content whole quantity of a curable resin composition, and it is more preferable to mix | blend in the ratio of 25-80 mass%.
Moreover, it is preferable to adjust so that solid content concentration of a green curable resin composition may be 5-70 mass% using a solvent.

(1) Photosensitive transparent resin composition The photosensitive transparent resin composition contains a photocurable resin that can be polymerized and cured by light such as ultraviolet rays and electron beams, and the exposed portion is cured to dissolve the unexposed portion. Examples of the negative photosensitive transparent resin composition that can be used to create a coating film pattern of only the exposed portion by removing.
In the green curable resin composition for a color filter of the present invention, the curable transparent resin composition is a negative photosensitive transparent resin composition, and a pattern can be easily formed using an existing process by a photolithography method. It is preferable because it can be formed.

  The negative photosensitive transparent resin composition containing a photocurable resin that can be polymerized and cured by light such as ultraviolet rays and electron beams is, for example, (i) an alkali-soluble resin, (ii) a polyfunctional monomer, (iii) It is composed of a photopolymerization initiator, a sensitizer and the like.

(I) Alkali-soluble resin As long as the alkali-soluble resin has a carboxyl group in the side chain, acts as a binder resin, and is soluble in a developer (particularly an alkali developer) used for pattern formation. There is no particular limitation.

  A preferable alkali-soluble resin is a resin having a carboxyl group, and specific examples thereof include an acrylic copolymer having a carboxyl group; an epoxy (meth) acrylate resin having a carboxyl group; and the like. Among these, particularly preferred are those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. It is because the film | membrane intensity | strength of the cured film formed improves by containing a photopolymerizable functional group. These acrylic copolymers and epoxy acrylate resins may be used in combination of two or more.

  The acrylic copolymer having a carboxyl group is obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer and an ethylenically unsaturated monomer. The acrylic copolymer having a carboxyl group may further contain a structural unit having an aromatic carbocyclic ring. The aromatic carbocycle functions as a component that imparts coating properties to the curable resin composition.

  The acrylic copolymer having a carboxyl group may further contain a structural unit having an ester group. The structural unit having an ester group functions as a component that suppresses alkali solubility of the photocurable resin composition.

  Moreover, as said acrylic copolymer containing a photopolymerizable functional group, glycidyl (meth) acrylate, 3,4-epoxy cyclohexylmethyl (meth) with respect to some carboxyl groups of the said acrylic copolymer. React the epoxy group of a compound having an epoxy group and an ethylenically unsaturated group in one molecule such as acrylate, 4- (2,3-epoxypropyl) butyl (meth) acrylate, allyl glycidyl ether, etc. A side chain obtained by 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 a part or all of the hydroxyl groups of the coalescence. An acrylic copolymer having an ethylenically unsaturated group can also be used.

The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the acrylic copolymer having a carboxyl group is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass.
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 having a carboxyl group 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 remarkably lowered, and when it is 500,000 or less, pattern formation can be facilitated during development with an alkaline developer.

  Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxyl group, The epoxy (meth) obtained by making the reaction material of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. Acrylate compounds are suitable.

  Examples of the epoxy compound include 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, and bisphenol fluorene type epoxy compounds. An epoxy compound is mentioned. 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.

(Ii) Polyfunctional monomer Examples of the polyfunctional monomer include di (meth) acrylates of alkylene glycol such as ethylene glycol and propylene glycol; di (meth) acrylates of polyalkylene glycol such as polyethylene glycol and polypropylene glycol ; Poly (meth) acrylates of polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. and their dicarboxylic acid modified products; polyesters, epoxy resins, urethane resins, alkyd resins, silicone resins , Oligo (meth) acrylates such as spirane resins; both terminal hydroxys such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene, both terminal hydroxypolycaprolactone, etc. And di (meth) acrylates of sulfonated polymers; tris (2- (meth) acryloyloxyethyl) phosphate, and the like.

  Of these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products are preferable. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tris. Succinic acid modified products of (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable. A polyfunctional monomer can be used individually or in mixture of 2 or more types.

The amount of the polyfunctional 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 alkali-soluble resin. By making the usage-amount of a polyfunctional monomer into 5 mass parts or more, it can prevent that pattern intensity | strength and the smoothness of a pattern surface fall. Moreover, by setting it as 500 mass parts or less, the fall of alkali developability can be prevented, for example, it can prevent that the soiling and film | membrane residue in areas other than the part in which a pattern is formed generate | occur | produce.
In addition, when not using alkali-soluble resin, it is preferable to set it as 4-75 mass parts with respect to 100 mass parts of non volatile matters of a photosensitive transparent resin composition, and it is more preferable to set it as 15-60 mass parts.

  In addition, a part of the polyfunctional monomer can be replaced with a monofunctional 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. A methacrylate etc. can be mentioned. Among these monofunctional monomers, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, methoxy Triethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate and the like are preferable. 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 monomer and the monofunctional monomer.

(Iii) Photopolymerization initiator and sensitizer The negative photosensitive transparent resin composition usually contains a photopolymerization initiator having activity with respect to the wavelength of the light source used. The photopolymerization initiator is appropriately selected in consideration of the difference in the reaction form of the photopolymerizable polymer or photopolymerizable monomer (for example, radical polymerization or cationic polymerization) and the type of each material.

  Examples of photopolymerization initiators are compounds that generate free radicals by the energy of ultraviolet rays, and include biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, and polynuclear quinone compounds. , Xanthone compounds, thioxanthone compounds, triazine compounds, ketal compounds, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds, fluoroamine compounds, etc. . These can be used alone or in combination.

Moreover, in this invention, at least any one of a sensitizer and a hardening accelerator can also be further used together with a photoinitiator as needed.
Specific examples of the sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethyl. Aminobenzoate, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  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.

(2) Thermosetting transparent resin composition As the thermosetting transparent resin composition, for example, an epoxy group or oxetanyl group and active hydrogen, a cyclic urea group and a hydroxyl group or the like, or a polyamic acid is heated. A polyimide precursor or the like that undergoes ring-closing imidization can be used.
As the thermosetting transparent resin composition, a combination of a compound having two or more thermosetting functional groups in one molecule and a curing agent is preferably used, and a catalyst capable of promoting a thermosetting reaction may be added. In addition, for the storage stability of the green curable resin composition, for example, a functional group that contributes to a thermal curing reaction such as blocking with a vinyl ether of carboxylic acid may be used on the active hydrogen side. . As the thermosetting functional group, an epoxy group or an oxetanyl group is preferably used. In addition, a polymer having no polymerization reactivity as described above may be further used.

  As a compound having two or more thermosetting functional groups in one molecule, an epoxy compound having two or more epoxy groups in one molecule is usually used. An epoxy compound having two or more epoxy groups in one molecule is an epoxy compound having two or more, preferably 2 to 50, more preferably 2 to 20 epoxy groups in one molecule (referred to as an epoxy resin). Is included). The epoxy group may be a structure having an oxirane ring structure, and examples thereof include a glycidyl group, an oxyethylene group, and an epoxycyclohexyl group. Examples of the epoxy compound include known polyvalent epoxy compounds that can be cured by carboxylic acid. Examples of such an epoxy compound include “Epoxy resin handbook” edited by Masaki Shinbo, published by Nikkan Kogyo Shimbun (Showa 62). Etc., and these can be used.

Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin , Fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, water Bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy Shi resin, glycidyl amine type epoxy resins, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin.
More specifically, bisphenol A type novolak epoxy resins such as trade name Epicoat 157S70 (manufactured by Japan Epoxy Resin Co., Ltd.) and cresol novolac type epoxy resins such as trade name YDCN-701 (manufactured by Tohto Kasei Co., Ltd.) can be mentioned. .

  As an epoxy compound, a polymer having a relatively high molecular weight that is usually used as a binder component in order to impart adhesion, heat resistance, and alkali resistance to a cured film (hereinafter sometimes referred to as “binder epoxy compound”), In order to increase the crosslinking density of the cured film or adjust the viscosity of the composition, the compound having a molecular weight smaller than that of the binder epoxy compound and having two or more epoxy groups in one molecule (hereinafter referred to as “multiple” You may use together with "the functional epoxy compound".

  The average molecular weight of the binder epoxy compound is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, when expressed in terms of polystyrene-equivalent weight average molecular weight. When the molecular weight of the binder epoxy compound is 1,000 or more, for example, it is possible to prevent physical properties such as strength and solvent resistance required for the cured resin layer as details of the color filter from becoming insufficient. On the other hand, when the molecular weight is 100,000 or less, it is possible to prevent the viscosity from being easily increased and the uniformity at the time of coating on the substrate to be impaired, so that a large distribution in the film thickness is likely to be generated.

  On the other hand, the weight average molecular weight in terms of polystyrene of the polyfunctional epoxy compound is preferably 4,000 or less, more preferably 3,000 or less, on condition that it is smaller than the binder epoxy compound combined therewith. In addition, a weight average molecular weight means the value calculated | required by polystyrene conversion using the gel permeation chromatography (For example, HLC-8029, Tosoh Corporation make) which used tetrahydrofuran as the developing liquid.

  The binder epoxy compound has a limit in the amount of epoxy that can be introduced into the copolymer molecule. When a polyfunctional epoxy compound having a relatively low molecular weight is added to the resin composition, epoxy groups are replenished in the composition, the reaction point concentration of the epoxy is increased, and the crosslinking density can be increased. The polyfunctional epoxy compound can be appropriately selected from the polyfunctional epoxy compounds described above.

  Moreover, as a hardening | curing agent, polyhydric carboxylic acid anhydride or polyhydric carboxylic acid is used, for example. The polyvalent carboxylic acid anhydride and the polyvalent carboxylic acid can be used singly or in combination of two or more. Further, for the storage stability of the green curable resin composition, a functional group that contributes to a thermosetting reaction such as blocking with a vinyl ether of a polyvalent carboxylic acid may be made latent.

  When the thermosetting functional group is an epoxy group, the amount of the curing agent is preferably in the range of 1 to 100 parts by mass per 100 parts by mass of the epoxy group-containing components (monomer and resin), and 5 to 50 More preferably, it is part by mass. When the blending amount of the curing agent is 1 part by mass or more, curing is sufficient and a tough coating film is easily formed. Moreover, it can prevent that the adhesiveness with respect to the board | substrate of a coating film is inferior that the compounding quantity of a hardening | curing agent is 100 mass parts or less, and can form a uniform and smooth coating film.

  In order to improve the hardness and heat resistance of the cured resin layer, for example, a catalyst capable of promoting a thermosetting reaction such as acid-epoxy may be added to the thermosetting transparent resin composition according to the present invention. As such a catalyst, a thermal latent catalyst that exhibits activity during heat curing can be used. The heat-latent catalyst exhibits catalytic activity when heated, accelerates the curing reaction and gives good properties to the cured product, and is added as necessary. The thermal latent catalyst is preferably one that exhibits acid catalytic activity at a temperature of 60 ° C. or higher. As such, a compound obtained by neutralizing a protonic acid with a Lewis base, a compound obtained by neutralizing a Lewis acid with a Lewis base, Lewis Examples thereof include a mixture of an acid and a trialkyl phosphate, sulfonic acid esters, onium compounds, and the like, and various compounds described in JP-A-4-218561 can be used. By combining such a catalyst with the above-mentioned blocked carboxylic acid, epoxy compound, and oxetanyl compound, it is possible to achieve both the storage stability of the curable resin composition and the lowering of the heat curing temperature.

<Other ingredients>
If necessary, the green curable resin composition for color filters according to the present invention may further contain a surfactant, an adhesion promoter, an ultraviolet absorber, a surface conditioner (leveling agent), or other components. May be.

(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 Co., Ltd.), Megafac (Dainippon Ink and Chemicals, )), 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.

(UV absorber)
For example, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like can be given.

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

<Method for producing green curable resin composition for color filter>
The green curable resin composition for a color filter of the present invention is mixed by introducing resin fine particles, a green pigment and a curable transparent resin composition into a solvent (single solvent or mixed solvent) together with other compounding components as necessary. The solid component can be dissolved or dispersed by a known dispersion method.

  However, in the above method, a large amount of green pigment and resin fine particles cannot be sufficiently dispersed in the solvent, and they may not have a desired dispersed particle size distribution. Therefore, a pigment dispersion as described above is prepared in advance, while a curable transparent resin composition in which other components such as resin fine particles and curable transparent resin composition are mixed, dispersed, or dissolved with a solvent is prepared. . The dispersed particle diameter of the green pigment in the green pigment dispersion and the resin fine particles in the curable transparent resin composition is measured with a laser scattering type particle size distribution measuring device Nanotrac UPA-EX150 (manufactured by Nikkiso), and there is no aggregation. After confirming the above, by mixing these green pigment dispersions and the curable transparent resin composition and performing a dispersion treatment as necessary, the green color for color filters having excellent pigment dispersibility and pigment dispersion stability over time A curable resin composition is easily obtained.

  If the pigment dispersion is not prepared in advance, first add the green pigment, resin fine particles and pigment dispersant into the solvent, mix well, stir to disperse the pigment, and remove coarse particles using centrifugation as appropriate. It is preferable to manufacture by adding and mixing the remaining components including the binder after the process. By blending a binder or the like after the pigment dispersion, not only the pigment dispersibility is not inhibited by the binder component and other blending components in the pigment dispersion step, but also the dispersion stability of the pigment is excellent.

<Curing film for color filter>
When the green curable resin composition thus obtained was a photosensitive resin composition and had alkali developability, the composition was applied to a support to form a coating film and dried. After that, after changing the solubility between the exposed part and the unexposed part, such as selectively curing a part of the coating film by irradiating the coating film with light in a predetermined pattern, developing with an alkaline solution By doing this, a cured film having a predetermined pattern is obtained.
In addition, when the green curable resin composition for a color filter is a thermosetting resin composition or does not have alkali developability, the composition is selectively printed on a predetermined region of the support or thermally transferred. After being adhered to the film, it is cured by heating or light irradiation to obtain a cured film having a predetermined pattern.

As a light beam used for the curing reaction, one having a wavelength that causes a reaction of the photosensitive resin composition is appropriately selected and used from radiation such as ultraviolet rays and ionizing radiation or visible light. Irradiation energy required for curing is typically, 10 to 500 mJ / m ² approximately. In the exposure step, a predetermined position of the coating film can be selectively exposed and cured by irradiating the surface of the coating film with laser light or irradiating light through a mask. Moreover, although the conditions of heat-curing differ with binders, it is normally dried at 50-200 degreeC using a vacuum dryer, oven, a hot plate, or other apparatuses to which heat is applied, and then about 120-400 degreeC. To improve the reliability.

[3. Color filter and display device]
The color filter of the present invention includes a colored layer formed using the green curable resin composition for a color filter of the present invention. By providing the colored layer, high optical performance can be realized while realizing a spectral spectrum necessary for the color filter.

  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.

  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 performance 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 this invention, the colored layer which shows a green pattern is formed using the said green curable resin composition of this invention. In particular, it is preferable to use a photosensitive resin composition containing an alkali-soluble binder resin because fine patterning is possible. This case will be described below as an example.

  In addition to the green curable resin composition of the present invention, red and blue curable resin compositions are prepared. Next, a certain color, for example, a red curable resin composition is applied on the transparent substrate 5 so as to cover the light shielding layer 6 by a known method such as spin coating to form a photosensitive red resin layer. The red colored layer 7R is formed by performing exposure through a photomask for use, and after alkali development and 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.

  As the red pigment and blue pigment contained in the curable resin composition for red and blue, known ones can be used, and various materials constituting the curable resin composition are also known. Things can be used.

  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), or an alloy 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. The 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.

  When the color filter 103 (display side substrate) thus obtained and the TFT array substrate (liquid crystal drive side substrate) are opposed to each other and the inner peripheral edge portions of both substrates are joined by 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>
<< Preparation of Green Pigment Dispersion >>
C. I. Pigment GREEN 58 green pigment (manufactured by DIC Corporation) (hereinafter referred to as “PG58”) 10 parts by mass, pigment dispersant (BYK2000, manufactured by BYK Chemie, nonvolatile content 40%) 10 parts by mass, propylene glycol monomethyl ether acetate (PGMEA) ) 65 parts by mass and 15 parts by mass of propylene glycol monomethyl ether were added to a 200 ml capacity mayonnaise bottle and mixed. Thereafter, 0.1 mm zirconia beads were added and dispersed for 2 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 green pigment dispersion having a volume average particle diameter (Mv) of 40 nm as a dispersion particle diameter of PG58 was obtained. I confirmed.

<< Preparation of photosensitive transparent resin composition >>
Multifunctional acrylate monomer (SR399E, Sakai Chemical) 13 parts by mass Binder resin: Methacrylic acid / Methyl methacrylate copolymer (Copolymerization ratio: 10/90 Acid value: 70 mg KOH / g Molecular weight: 9000)
0 parts by mass cross-linked acrylic resin fine particles MG-152 (manufactured by Nippon Paint)
(Average particle size 70 nm) 2.4 parts by mass Solvent: PGMEA (manufactured by Daicel Chemical Industries) 80 parts by mass Initiator: Irgacure 907 (manufactured by Ciba Specialty Chemicals) 3 parts by mass Sensitizer: 1.6 parts by mass of diethylaminobenzophenone

  The above was mixed and stirred to obtain a photosensitive transparent resin composition having a nonvolatile content of 20% by mass (the resin fine particles corresponding to 100% by mass of the nonvolatile component corresponded to 12 parts by mass). Moreover, as a result of measuring this photosensitive transparent resin composition with a laser scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso), it was confirmed that the volume average particle diameter (Mv) of MG-152 was 73 nm. did it. This confirmed that MG-152 was dispersed without agglomeration.

<< Preparation of green curable resin composition >>
Green pigment dispersion liquid 7 mass parts photosensitive transparent resin composition 4 mass parts KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.02 mass parts MegaFac R-08MH (manufactured by Dainippon Ink and Chemicals) 0.02 mass parts PGMEA 1 mass Part

  The above was mixed and the green curable resin composition (green curable resin composition for color filters) was prepared.

The obtained green curable resin composition was spin-coated on a glass substrate so that the chromaticity y with a C light source after drying was 0.5, and heated at 80 ° C. for 3 minutes to give a green curable resin composition A dry film of the product was formed. The film was exposed to 60 mJ / m ^{2 of} ultraviolet light with a high-pressure mercury lamp and cured.

As a result of measuring the universal hardness of the cured coating film using a micro hardness meter (Fischer, Vickers indenter, 20 mN / 10 sec pressure), the hardness of the coating film was 264 N / mm ² . Furthermore, post-baking was performed at 230 ° C. for 30 minutes after exposure to obtain a substrate for color filter evaluation. The universal hardness of this substrate was 558 N / mm ² .
When the thermal weight reduction of the dried coating film piece of the green curable resin composition after the exposure was measured, it was 3.2% at the temperature at the post-baking time.
In addition, Shimadzu Corporation DTG-60A was used for the measurement of thermogravimetry, the measurement temperature range was 230 degreeC from room temperature, and the temperature increase rate was 10 degrees C / min.

<Example 2>
In “Preparation of photosensitive transparent resin composition” in Example 1,
Binder resin: methacrylic acid / methyl methacrylate copolymer (copolymerization ratio: 10/90 acid value: 70 mg KOH / g molecular weight: 9000)
1.2 parts by mass cross-linked acrylic resin fine particles MG-152 (average particle size 70 nm) A green curable resin composition (photosensitive transparent resin composition) was prepared in the same manner as in Example 1 except that the content was changed to 1.2 parts by mass. The resin fine particles with respect to 100 parts by mass of the non-volatile content correspond to 6 parts by mass). Using this, a coating film was formed in the same manner as in Example 1, and film hardness measurement and thermal weight loss measurement were performed. Hardness of the coating film after exposure 225N / mm ^2, the universal hardness after post-baking was 560N / mm ^2.
When the thermal weight loss of the dried coating film piece of the green curable resin composition after exposure was measured, it was 3.5% at the temperature at the time of post-baking.

<Example 3>
In “Preparation of photosensitive transparent resin composition” in Example 1,
Binder resin: methacrylic acid / methyl methacrylate copolymer (copolymerization ratio: 10/90 acid value: 70 mg KOH / g molecular weight: 9000) 0 parts by mass cross-linked acrylic resin fine particles MG-161 (manufactured by Nippon Paint) (average particle diameter 100nm)
A green curable resin composition (corresponding to 12 parts by mass of resin fine particles with respect to 100 parts by mass of the nonvolatile content of the photosensitive transparent resin composition) was prepared in the same manner as in Example 1 except that the amount was changed to 2.4 parts by mass. . Using this, a coating film was formed in the same manner as in Example 1, and film hardness measurement and thermal weight loss measurement were performed. Hardness of the coating film after exposure is 257N / mm ^2, the universal hardness after post-baking was 550 N / mm ^2.
When the thermal weight loss of the dried coating film piece of the green curable resin composition after exposure was measured, it was 3.4% at the post-baking temperature.

<Example 4>
In “Preparation of photosensitive transparent resin composition” in Example 1,
Binder resin: methacrylic acid / methyl methacrylate copolymer (copolymerization ratio: 10/90 acid value: 70 mg KOH / g molecular weight: 9000)
1.2 parts by mass cross-linked acrylic resin fine particles MG-161 (manufactured by Nippon Paint) (average particle size 100 nm) A green curable resin composition (photosensitive material) was obtained in the same manner as in Example 1 except that the amount was changed to 1.2 parts by mass. The resin fine particles with respect to 100 parts by mass of the nonvolatile content of the transparent conductive resin composition corresponded to 6 parts by mass). Using this, a coating film was formed in the same manner as in Example 1, and film hardness measurement and thermal weight loss measurement were performed. The hardness of the coating film after exposure was 237 N / mm ² , and the universal hardness after post-baking was 549 N / mm ² .
When the thermal weight reduction of the dried coating film piece of the green curable resin composition after exposure was measured, it was 3.6% at the temperature at the time of post-baking.

(Comparative Example 1)
Binder resin: methacrylic acid / methyl methacrylate copolymer (copolymerization ratio: 10/90 acid value: 70 mgKOH / g molecular weight: 9000) in “Preparation of photosensitive transparent resin composition” in Example 1
2.4 parts by mass cross-linked acrylic resin fine particles MG-152 (manufactured by Nippon Paint) A green curable resin composition was produced in the same manner as in Example 1 except that the amount was changed to 0 parts by mass. Using this, a coating film was formed in the same manner as in Example 1, and film hardness measurement and thermal weight loss measurement were performed. Hardness of the coating film after exposure 206N / mm ^2, the universal hardness after post-baking was 534N / mm ^2.
When the thermal weight loss of the dried coating film piece of the green curable resin composition after exposure was measured, it was 3.8% at the temperature at the time of post-baking.

  From the above, it was found that by adding fine particles, the coating film hardness at the time of post-baking of the green color filter can be improved, and thereby the decrease in thermal weight can be suppressed.

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 (6)

  A green curable resin composition for a color filter, comprising a green pigment, a curable transparent resin composition, and resin fine particles.   The green curable resin composition according to claim 1, wherein the resin fine particles are blended in an amount of 5 to 50 parts by mass with respect to 100 parts by mass of the nonvolatile content of the curable transparent resin composition.   The green curable resin composition according to claim 1 or 2, wherein the resin fine particles are acrylic resin fine particles containing (meth) acrylic acid and an ester thereof as a structural unit.   The green curable resin composition according to any one of claims 1 to 3, wherein the resin fine particles have an average particle size of 10 to 200 nm.   The color filter provided with the colored layer formed using the green curable resin composition for color filters of any one of Claims 1-4.   A display device comprising the color filter according to claim 5.

Images