JP2011164646A - Resin composition for inkjet type color filter, color filter and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for an inkjet type color filter, which has excellent dispersion stability, is hardly dried, and is excellent in ink discharge performance. <P>SOLUTION: The resin composition for an inkjet type color filter contains (A) a pigment, (B) a dispersant, (C) a solvent having two acetate structures, (D) a polyfunctional monomer, and (E) a binder resin, wherein the use ratio of (C) the solvent having two acetate structures to the entire solvent is 46-100 wt.%. A color filter having a pixel pattern formed by inkjet using the resin composition for an inkjet type color filter, and a liquid crystal display device including the color filter are provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a resin composition for producing a color filter used in a color liquid crystal display device or a color image pickup tube element by an ink jet method, and a color having a pixel pattern formed from the resin composition for a color filter by an ink jet method. The present invention relates to a filter and a liquid crystal display device.

In producing a color filter used for a color liquid crystal display (LCD) or the like, a colored radiation-sensitive composition film is usually formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed. By irradiating with radiation through a photomask having the pattern shape (hereinafter referred to as “exposure”), developing and dissolving and removing unexposed portions, and then post-baking using a clean oven or hot plate A method of forming a pixel pattern of each color (see Patent Document 1 and Patent Document 2) is known. However, these methods have problems such as a complicated pixel pattern forming process and high cost.

On the other hand, Patent Documents 3 to 5 propose a method for producing an ink-jet color filter and a resin composition for an ink-jet color filter, which include a step of forming a colored layer of a color filter using an ink-jet head. Yes.
However, with the recent spread of high-definition televisions and the like, there is an increasing demand for color liquid crystal display elements to have a high color density. In addition, improvement in productivity is required for the purpose of cost reduction. For this reason, in the ink jet type color filter manufacturing method, it is required to reduce the time for ejecting ink. In order to satisfy these requirements, it is necessary to increase the pigment concentration and the solid content concentration of the ink. Along with this, when the pigment concentration is increased, the content of the pigment in the ink is increased, so that a high boiling point solvent contained in the ink causes a large amount of foreign matter such as precipitates generated by destroying the pigment dispersion system. Therefore, there has been a problem that ink discharge failure occurs. When the concentration of solids is increased, the amount of the high boiling point solvent contained in the ink is reduced, so that the ink is easy to dry. There was a problem of letting. In addition, in the case of an ink that is required to have both a high pigment concentration and a high solid content concentration, both problems of increasing foreign matters and facilitating drying occurred at the same time.
Therefore, development of a resin composition for an inkjet color filter that has good dispersion stability and is difficult to dry is strongly demanded.

JP-A-2-144502 JP-A-3-53201 JP-A-4-261503 JP 7-318723 A JP 2000-310706 A

An object of the present invention is to provide a resin composition for an ink jet color filter that has good dispersion stability, is difficult to dry, and has excellent ink ejection properties.
The other subject of this invention is providing the color filter formed from the said composition of this invention.
Still another object of the present invention is to provide a liquid crystal display device provided with the color filter of the present invention.
Other problems and advantages of the present invention will be apparent from the following description.

The present invention comprises (A) a pigment, (B) a dispersant, (C) a solvent having two acetate structures, (D) a polyfunctional monomer, and (E) a binder resin. C) A resin composition for an ink-jet color filter, wherein the proportion of the solvent having two acetate structures is 46 to 100% by weight based on the whole solvent.
Moreover, this invention is a resin composition for inkjet system color filters of Claim 1 whose usage-amount of the said (C) solvent which has two acetate structures is 73 to 100 weight% with respect to the whole solvent. It is.
Moreover, this invention is a color filter characterized by having the pixel pattern formed by the inkjet system using the said resin composition for inkjet system color filters.
Further, the present invention is a liquid crystal display device comprising the color filter.

The resin composition for ink-jet color filters of the present invention has good dispersion stability, is difficult to dry, and is excellent in ink ejection properties.

It is a principal part longitudinal cross-sectional view which illustrates the manufacturing process of the color filter in this invention, (a) is a partition formation process, (b) is a pixel pattern formation process, (c) is a drying process, (d) is protection. The layer forming step and (e) show the common electrode forming step. It is a principal part longitudinal cross-sectional view which illustrates the liquid crystal display device which has the color filter manufactured by the manufacturing method of the color filter in this invention. It is a top view of the color filter manufactured by the manufacturing method of the color filter in this invention. It is a figure which illustrates the outline | summary of the color filter manufacturing apparatus used for the manufacturing method of the color filter in this invention. It is a partial cross section which illustrates the principal part of the inkjet head used for the manufacturing method of the color filter in this invention. It is a top view which illustrates the arrangement | positioning of each nozzle in the inkjet head used for the manufacturing method of the color filter in this invention, and the filter element in the board | substrate with which the partition was formed.

Hereinafter, the present invention will be described in detail.
Pigment dispersion composition [ink-jet color filter (radiation sensitive) resin composition]
-(A) Pigment-
The pigment in the present invention is not particularly limited, and may be an organic pigment or an inorganic pigment. Of these, organic pigments are particularly preferred because color filters are required to have high-purity and highly transparent color development and heat resistance.

Examples of the organic pigment include, for example, compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C.I. ) Can be listed.
C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 211;

C. I. Pigment orange 36, C.I. I. Pigment orange 43, C.I. I. Pigment orange 51, C.I. I. Pigment orange 61, C.I. I. Pigment orange 71;
C. I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 207, C.I. I. Pigment red 208, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254;
C. I. Pigment violet 19, pigment violet 23, pigment violet 29;
C. I. Pigment blue 15, C.I. I. Pigment blue 60, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 136, C.I. I. Pigment green 210;
C. I. Pigment brown 23, C.I. I. Pigment Brown 25.
These organic pigments can be used alone or in admixture of two or more.

  In the present invention, the organic pigment can be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof.

Examples of the inorganic pigment include, for example, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean [red iron oxide (III)], cadmium red, ultramarine blue, bitumen, and chromium oxide. Examples include green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.
These inorganic pigments can be used alone or in admixture of two or more.

Furthermore, in the present invention, if necessary, one or more dyes or natural pigments can be used in combination with the pigment.
In the present invention, the pigment can be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the particle surface of the pigment include the polymers described in JP-A-8-259876 and various commercially available polymers or oligomers for dispersing pigments.

-(B) Dispersant-
As the dispersant in the present invention, for example, an appropriate dispersant such as cationic, anionic, nonionic or amphoteric can be used, but a compound having a urethane bond (hereinafter referred to as “urethane-based dispersant”). A dispersant containing is preferred.
The urethane bond is generally of the formula R—NH—COO—R ′ (where R and R ′ are aliphatic, alicyclic or aromatic monovalent or polyvalent organic groups, The group is further bonded to a group having another urethane bond or to another group.) And can be present in a lipophilic group and / or a hydrophilic group in the urethane-based dispersant. It can be present in the main chain and / or side chain of the dispersant, and more than one can be present in the urethane-based dispersant. When two or more urethane bonds are present in the urethane-based dispersant, each urethane bond may be the same or different.

Examples of such urethane dispersants include reaction products of diisocyanates and / or triisocyanates with polyesters having a hydroxyl group at one end and / or polyesters having a hydroxyl group at both ends. be able to.
Examples of the diisocyanates include benzene diisocyanates such as benzene-1,3-diisocyanate and benzene-1,4-diisocyanate; toluene-2,4-diisocyanate, toluene-2 , 5-diisocyanate, toluene-2,6-diisocyanate, toluene diisocyanates such as toluene-3,5-diisocyanate; 1,2-xylene-3,5-diisocyanate, 1, 2-xylene-3,6-diisocyanate, 1,3-xylene-2,4-diisocyanate, 1,3-xylene-2,5-diisocyanate, 1,3-xylene-4,6- Other than xylene diisocyanates such as diisocyanate, 1,4-xylene-2,5-diisocyanate, 1,4-xylene-2,6-diisocyanate And the like aromatic diisocyanates.

Examples of the triisocyanates include benzene such as benzene-1,2,4-triisocyanate, benzene-1,2,5-triisocyanate, and benzene-1,3,5-triisocyanate. Triisocyanates; toluene-2,3,5-triisocyanate, toluene-2,3,6-triisocyanate, toluene-2,4,5-triisocyanate, toluene-2,4,6-tri Toluene isocyanates such as isocyanate; 1,2-xylene-3,4,5-triisocyanate, 1,2-xylene-3,4,6-triisocyanate, 1,3-xylene-2, 4,5-triisocyanate, 1,3-xylene-2,4,6-triisocyanate, 1,3-xylene-4,5,6-triisocyanate, 1,4 And other aromatic triisocyanates such as xylene triisocyanates such as xylene-2,3,5-triisocyanate and 1,4-xylene-2,3,6-triisocyanate. .
These diisocyanates and triisocyanates can be used alone or in admixture of two or more.

Examples of the polyester having a hydroxyl group at one end and the polyester having a hydroxyl group at both ends include, for example, polycaprolactone having a hydroxyl group at one end or both ends, polyvalerolactone having a hydroxyl group at one end or both ends, and one end Or a polylactone having a hydroxyl group at one or both ends, such as polypropiolactone having a hydroxyl group at both ends; polyethylene terephthalate having a hydroxyl group at one or both ends, polybutylene terephthalate having a hydroxyl group at one or both ends, etc. Examples thereof include polycondensed polyesters having a hydroxyl group at one or both ends.
These polyesters having a hydroxyl group at one end and polyesters having a hydroxyl group at both ends can be used alone or in admixture of two or more.

The urethane-based dispersant in the present invention is preferably a reaction product of an aromatic diisocyanate and a polylactone having a hydroxyl group at one end and / or a polylactone having a hydroxyl group at both ends, particularly toluene diisocyanate. A reaction product of a polycaprolactone having a hydroxyl group at one end and / or a polycaprolactone having a hydroxyl group at both ends is preferred.
Specific examples of such urethane-based dispersants are trade names such as Disperbyk161, Disperbyk170 (by Big Chemie (BYK)), EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disparon (Enomoto Kasei Co., Ltd.) ))) Series.
The weight average molecular weight (Mw) of the urethane-based dispersant in the present invention is usually 5,000 to 50,000, preferably 7,000 to 20,000.
The said urethane type dispersing agent can be used individually or in mixture of 2 or more types.

A (meth) acrylic dispersant composed of a (co) polymer of (meth) acrylic monomers is also preferred as the dispersant.
Specific examples of such (meth) acrylic dispersants include Dysperbyk 2000 and Dysperbyk 2001 (above, manufactured by BYK Corporation) under the trade names.
The said (meth) acrylic-type dispersing agent can be used individually or in mixture of 2 or more types.

The amount of the dispersant used in preparing the pigment dispersion is usually 100 parts by weight or less, preferably 0.5 to 100 parts by weight, more preferably 1 to 70 parts by weight, particularly 100 parts by weight of the pigment. Preferably it is 10-50 weight part. In this case, if the amount of the dispersant used exceeds 100 parts by weight, developability and the like may be impaired.

Moreover, as a solvent used when preparing a pigment dispersion liquid, the thing similar to the solvent illustrated about the liquid composition of the resin composition mentioned later can be mentioned, for example.
The amount of the solvent used in preparing the pigment dispersion is usually 500 to 1,000 parts by weight, preferably 700 to 900 parts by weight with respect to 100 parts by weight of the pigment.

When preparing a pigment dispersion using a bead mill, for example, glass beads or titania beads having a diameter of about 0.5 to 10 mm are used, and a pigment mixture composed of a pigment, a solvent and a dispersant is used. Preferably, it can be carried out by mixing and dispersing while cooling with cooling water or the like.
In this case, the filling rate of the beads is usually 50 to 80% of the mill capacity, and the injection amount of the pigment mixed solution is usually about 20 to 50% of the mill capacity. The treatment time is usually 2 to 50 hours, preferably 2 to 25 hours.

Moreover, when preparing using a roll mill, it can carry out by processing, for example, using a 3 roll mill, a 2 roll mill, etc., preferably cooling a pigment liquid mixture with cooling water etc.
In this case, the roll interval is preferably 10 μm or less, and the shearing force is usually about 108 dyn / second. The treatment time is usually 2 to 50 hours, preferably 2 to 25 hours.

-(C) Solvent having two acetate structures-
Examples of the solvent having two acetate structures in the present invention include propylene glycol diacetate and 1,3-butylene glycol diacetate, and 1,3-butylene glycol diacetate has dispersion stability and drying properties. It is particularly preferable from the viewpoint.

In the present invention, other solvents can be used in combination.
Examples of such other solvents include:
Alcohols such as methanol, ethanol, benzyl alcohol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, di Propylene glycol mono- - butyl ether, tripropylene glycol monomethyl ether, such as tripropylene glycol monoethyl ether (poly) alkylene glycol monoalkyl ether;

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

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

Among these solvents, benzyl alcohol, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol from the viewpoints of solubility, pigment dispersibility, coatability, etc. Mono-n-butyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, n-butyl acetate I-butyl acetate, n-pentyl formate, i-pentyl acetate, 3- Toxibutyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3- Methoxybutyl propionate, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Further, together with the above solvent, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ- A high boiling point solvent such as butyrolactone, ethylene carbonate, propylene carbonate, or ethylene glycol monophenyl ether acetate can be used in combination.

  The use ratio of the other solvent is preferably 0 to 40% by weight with respect to the total amount of (C) the solvent having two acetate structures and the other solvent. In this case, if the use ratio of the other solvent exceeds 40% by weight, the ink is liable to be dried, so that a dry matter is liable to be generated, and the pigment dispersion is liable to be destroyed, so that a precipitate is liable to be generated. There is.

  The amount of the solvent used is preferably 5 to 35% by weight, more preferably the total concentration of each component excluding the solvent of the composition, from the viewpoints of ink ejection properties and storage stability of the resin composition obtained. Is preferably 10 to 20% by weight.

-(D) polyfunctional monomer-
The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds.
As the multifunctional monomer, for example,
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Poly (meth) acrylates of polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol, and their dicarboxylic acid modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of hydroxylated polymers at both ends such as both ends hydroxypoly-1,3-butadiene, both ends hydroxypolyisoprene, both ends hydroxypolycaprolactone,
And tris [2- (meth) acryloyloxyethyl] phosphate.

Among these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid modified products, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meta) ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are preferred, especially trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate. However, it is preferable in that it is excellent in pixel strength and surface smoothness, and hardly causes scumming or film residue on the unexposed substrate and the light shielding layer.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

The amount of the polyfunctional monomer used in the present invention is preferably 5 to 1,000 parts by weight, more preferably 20 to 300 parts by weight with respect to 100 parts by weight of the (A) pigment. In this case, if the amount of the polyfunctional monomer used is less than 5 parts by weight, the strength and surface smoothness of the pixel tend to decrease, while if it exceeds 1,000 parts by weight, the pigment concentration decreases relatively. Therefore, it may be difficult to achieve a target color density as a thin film.

-(E) Binder resin-
As the binder resin in the present invention, an appropriate resin can be used as long as it functions as a binder for (A) the pigment.
A preferred binder resin in the present invention is a polymer containing a carboxyl group, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter simply referred to as “carboxyl group-containing unsaturated monomer”). ) And another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as “other unsaturated monomer (e1)”) (hereinafter referred to as “carboxyl group-containing copolymer (E1)”. ) ").

As the carboxyl group-containing unsaturated monomer, for example,
Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids (anhydrides) such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; Things);
2 such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) Mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids having higher valences;
Examples thereof include mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate.
Succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are commercially available under the trade names M-5300 and M-5400 (manufactured by Toagosei Co., Ltd.), respectively. Has been.
These carboxyl group-containing ethylenically unsaturated monomers can be used alone or in admixture of two or more.

Moreover, as another unsaturated monomer (e1), for example,
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m Aromatic vinyl compounds such as vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether;
Indenes such as indene and 1-methylindene;

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl Methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl Acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy Tyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate , 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate , Toxipropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy- Unsaturated carboxylic esters such as 3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate;

2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl Unsaturated alkylaminoalkyl esters such as methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;

Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidyl ether;
Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides or unsaturated imides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamide, and maleimide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples include macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. be able to.
These other unsaturated monomers (e1) can be used alone or in admixture of two or more.

  As the carboxyl group-containing copolymer (E1), (1) acrylic acid and / or methacrylic acid and (2) styrene, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl A copolymer with at least one selected from the group of methacrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer is preferred.

As a specific example of the preferred carboxyl group-containing copolymer (E1),
Acrylic acid / benzyl acrylate copolymer, acrylic acid / styrene / methyl acrylate copolymer, acrylic acid / styrene / benzyl acrylate copolymer, acrylic acid / methyl acrylate / polystyrene macromonomer copolymer, acrylic acid / methyl acrylate / Polymethylmethacrylate macromonomer copolymer, acrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polystyrene Macromonomer copolymer, acrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polymethyl methacrylate macromonomer copolymer,

Acrylic acid / benzyl methacrylate copolymer, acrylic acid / styrene / methyl methacrylate copolymer, acrylic acid / styrene / benzyl methacrylate copolymer, acrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / methyl methacrylate / Polymethyl methacrylate macromonomer copolymer, acrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene Macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate mac Acrylic acid copolymers such as monomer copolymers;

Methacrylic acid / benzyl acrylate copolymer, methacrylic acid / styrene / methyl acrylate copolymer, methacrylic acid / styrene / benzyl acrylate copolymer, methacrylic acid / methyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / methyl acrylate / Polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polystyrene Macromonomer copolymer, methacrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polymethyl methacrylate Ma copolymer,

Methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / styrene / methyl methacrylate copolymer, methacrylic acid / styrene / benzyl methacrylate copolymer, methacrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / methyl methacrylate / Polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene Macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl Methacrylic acid copolymers such as Takuri rate macromonomer copolymers and the like.

Among these carboxyl group-containing copolymers (E1), methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / styrene / methyl methacrylate copolymer, methacrylic acid / styrene / benzyl methacrylate copolymer, methacrylic acid / Methyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer Polymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / 2-hydroxy Chill methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymers.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer (E1) is usually 5 to 50% by weight, preferably 10 to 40% by weight.
In this invention, a carboxyl group-containing copolymer (E1) can be used individually or in mixture of 2 or more types.

Another preferable binder resin in the present invention is an N-substituted maleimide and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as “other unsaturated monomer (e2)”). (Hereinafter referred to as “N-substituted maleimide copolymer (E2)”).
Examples of the N-substituent in the N-substituted maleimide include a (Cyclo) alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, and these groups. Among these N-position-substituents, aryl groups having 6 to 20 carbon atoms and substituted derivatives thereof are preferable.

Specific examples of the N-substituted maleimide include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Nt-butylmaleimide, N N- (cyclo) alkyl-substituted maleimides such as n-pentylmaleimide, Nn-hexylmaleimide, N-cyclohexylmaleimide, N-4-methylcyclohexylmaleimide, N-4-chlorocyclohexylmaleimide, and substitution thereof Derivatives;

N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methyl N-aryl-substituted maleimides such as phenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, Np-chlorophenylmaleimide, and substituted derivatives thereof;

N-benzylmaleimide, N-phenethylmaleimide, N-o-hydroxybenzylmaleimide, Nm-hydroxybenzylmaleimide, Np-hydroxybenzylmaleimide, N-o-methylbenzylmaleimide, Nm-methylbenzylmaleimide, N-aralkyl-substituted maleimides such as Np-methylbenzylmaleimide, N-o-methoxybenzylmaleimide, Nm-methoxybenzylmaleimide, Np-methoxybenzylmaleimide, Np-chlorobenzylmaleimide, These substituted derivatives can be mentioned.

Among these N-substituted maleimides, N-cyclohexylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenyl Maleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide are preferable.
The N-substituted maleimides can be used alone or in admixture of two or more.

The other unsaturated monomer (e2) is not limited as long as it can be copolymerized with the N-substituted maleimide, but one or more of the carboxyl group-containing unsaturated monomers and the other A monomer mixture containing at least one unsaturated monomer (e1) is preferred.

The N-substituted maleimide copolymer (E2) is preferably a copolymer of N-phenylmaleimide, more preferably N-phenylmaleimide, a carboxyl group-containing unsaturated monomer, and other unsaturated monomers ( e1), especially (1) N-phenylmaleimide, (2) acrylic acid and / or methacrylic acid, (3) styrene, (4) methyl acrylate, methyl methacrylate, 2 -Copolymerization with at least one selected from the group consisting of hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer Coalescence is preferable.

Specific examples of preferred N-substituted maleimide copolymers (E2) include
N-phenylmaleimide / methacrylic acid / styrene / allyl acrylate copolymer, N-phenylmaleimide / methacrylic acid / styrene / allyl methacrylate copolymer, N-phenylmaleimide / methacrylic acid / styrene / benzyl methacrylate copolymer, N -Phenylmaleimide / methacrylic acid / styrene / phenyl methacrylate copolymer,
N-phenylmaleimide / methacrylic acid / styrene / benzyl methacrylate / polystyrene macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, N-phenylmaleimide / methacrylic acid / Styrene / phenyl methacrylate / polystyrene macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / phenyl methacrylate / polymethyl methacrylate macromonomer copolymer,

N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer Copolymer, N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / phenyl methacrylate / polystyrene macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / phenyl methacrylate / poly Examples thereof include a methyl methacrylate macromonomer copolymer.

The copolymerization ratio of N-substituted maleimide in the N-substituted maleimide copolymer (E2) is usually 5 to 50% by weight, preferably 10 to 40% by weight.
When the N-substituted maleimide copolymer is a copolymer of an N-substituted maleimide, a carboxyl group-containing unsaturated monomer, and another unsaturated monomer (e1), the carboxyl group-containing unsaturated The copolymerization ratio of the monomer is usually 5 to 50% by weight, preferably 10 to 40% by weight, and the copolymerization ratio of the other unsaturated monomer (e1) is usually 10 to 90% by weight. , Preferably 20 to 80% by weight.
In the present invention, the N-position-substituted maleimide copolymer (E2) can be used alone or in admixture of two or more.

  The polystyrene-converted weight average molecular weight (hereinafter simply referred to as “weight average molecular weight”) measured by gel permeation chromatography (GPC; elution solvent tetrahydrofuran) of each resin component constituting the binder resin in the present invention is preferably 3, 000 to 300,000, particularly preferably 5,000 to 100,000.

  The ratio of the binder resin used in the present invention is usually 0 to 1,000 parts by weight, preferably 20 to 500 parts by weight, per 100 parts by weight of the (A) pigment. In this case, if the amount exceeds 1,000 parts by weight, the pigment concentration relatively decreases, and it may be difficult to achieve the target color concentration as a thin film.

-(F) Photopolymerization initiator-
The (radiation sensitive) resin composition of this invention can mix | blend (F) photoinitiator. The photopolymerization initiator in the present invention is the above-mentioned (D) polyfunctional monomer and a monofunctional monomer used in some cases upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound capable of generating an active species capable of initiating polymerization of the body.
Examples of such photopolymerization initiators include acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds. A compound etc. can be mentioned.

  In the present invention, the photopolymerization initiator can be used alone or in admixture of two or more. As the photopolymerization initiator in the present invention, acetophenone compounds, biimidazole compounds and triazine compounds can be used. At least one selected from the group is preferred.

Among preferred photopolymerization initiators in the present invention, specific examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropanone-1, 2-methyl-1- (4-methylthiophenyl) -2. -Morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,1-hydroxycyclohexyl phenylketone, 2,2-dimethoxy-1,2-diphenylethanone -1 etc. can be mentioned.
Among these acetophenone compounds, in particular, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone -1 or the like is preferable.
The acetophenone compounds can be used alone or in admixture of two or more.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-bi. Imidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetra Phenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2, 2'-bis (2-bromophenyl)- , 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1, Examples include 2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, and the like. .

Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole and the like are more preferable, and in particular, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 '-Biimidazole is preferred.
The above biimidazole compounds can be used alone or in admixture of two or more.

-Hydrogen donor-
In the present invention, when a biimidazole compound is used as a photopolymerization initiator, it is preferable to use the following hydrogen donor in combination because the sensitivity can be further improved.
The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
The hydrogen donor in the present invention is preferably a mercaptan compound or an amine compound as defined below.

The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ Mercaptan-based hydrogen donor ").
The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound”). , "Amine-based hydrogen donor").
These hydrogen donors can also have a mercapto group and an amino group at the same time.

Hereinafter, these hydrogen donors will be described more specifically.
The mercaptan-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, It may or may not be formed.
In addition, when the mercaptan hydrogen donor has two or more mercapto groups, at least one of the remaining mercapto groups is substituted with an alkyl, aralkyl or aryl group as long as at least one free mercapto group remains. Furthermore, as long as at least one free mercapto group remains, a structural unit in which two sulfur atoms are bonded via a divalent organic group such as an alkylene group, or two sulfur atoms are It can have structural units linked in the form of disulfides.

Furthermore, the mercaptan-based hydrogen donor may be substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like at a place other than the mercapto group.
Specific examples of such mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto- Examples include 2,5-dimethylaminopyridine.
Of these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and the like are preferable, and 2-mercaptobenzothiazole is particularly preferable.

Next, the amine-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When these two or more rings are present, A condensed ring may or may not be formed.
In addition, in the amine-based hydrogen donor, one or more of the amino groups may be substituted with an alkyl group or a substituted alkyl group, and a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxy group may be substituted at a position other than the amino group. It may be substituted with a carbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like.

Specific examples of such amine-based hydrogen donors include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, Examples thereof include ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
Of these amine-based hydrogen donors, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone and the like are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amine-based hydrogen donor has a function as a sensitizer even in the case of a photopolymerization initiator other than a biimidazole compound.

  In the present invention, the hydrogen donor can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the formed pixels are difficult to drop off from the substrate during development, and that the pixels have high strength and sensitivity.

Specific examples of a preferred combination of a mercaptan hydrogen donor and an amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-. Bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone and the like, and more preferable combinations Are 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and the particularly preferred combination is 2-mercaptoben Thiazole / 4,4'-bis (diethylamino) benzophenone.
The weight ratio of mercaptan hydrogen donor to amine hydrogen donor in the combination of mercaptan hydrogen donor and amine hydrogen donor is preferably 1: 1 to 1: 4, more preferably 1: 1 to 1. : 3.

Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine compounds having a halomethyl group, such as cistyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.
Of these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine is particularly preferable.
The above triazine compounds can be used alone or in admixture of two or more.

-Additive component-
The radiation sensitive composition for a color filter in the present invention may contain various additive components as necessary.

As the additive component, for example,
Dispersion aids such as blue pigment derivatives and yellow pigment derivatives such as copper phthalocyanine derivatives;
Fillers such as glass and alumina;
Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ether, poly (fluoroalkyl acrylate);
Nonionic, cationic and anionic surfactants;

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

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

The following product names are F-top EF301, EF303, EF352 (above, Shin-Akita Kasei Co., Ltd.), MegaFuck F171, F172, F173, F173K (above, Dainippon Ink & Chemicals, Inc.) ), FLORAD FC430, FC431 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-104 105, SC-106 (manufactured by Asahi Glass Co., Ltd.), KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (above, manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and the like.

Furthermore, the resin composition for an ink jet color filter in the present invention can contain a thermal acid generator and an acid crosslinking agent.
The thermal acid generator is a component that generates an acid by heating, and examples thereof include onium salts such as sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts, and particularly sulfonium salts. And benzothiazolium salts are preferred.
As the sulfonium salt, a compound represented by the following formula (1) (hereinafter referred to as “sulfonium salt (1)”) is preferable.

R ²
/
R ¹ -S · Y ⁻ (1)
\
R ³

[In the formula (7), R ¹ , R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 5 carbon atoms or a substituted derivative thereof, or an aryl group having 6 to 10 carbon atoms or a substituted derivative thereof. And at least one of R ¹ , R ² and R ³ is an aryl group having 6 to 10 carbon atoms or a substituted derivative thereof, and Y ⁻ represents a monovalent anion. ]

Specific examples of the sulfonium salt (1) include
4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, 4-benzyloxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate, 4-benzoyloxyphenyldimethylsulfonium hexafluoroantimonate, 4- Dialkylsulfonium salts such as benzoyloxyphenyldimethylsulfonium hexafluoroarsenate, 3-chloro-4-acetoxyphenyldimethylsulfonium hexafluoroantimonate;

4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate, 4-hydroxyphenylbenzylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, 4-methoxyphenylbenzylmethylsulfonium hexafluoroantimonate, 2-methyl Monobenzylsulfonium salts such as -4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate and 3-chloro-4-hydroxyphenylbenzylmethylsulfonium hexafluoroarsenate;

4-hydroxyphenyldibenzylsulfonium hexafluoroantimonate, 4-hydroxyphenyldibenzylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, 4-methoxyphenyldibenzylsulfonium hexafluoroantimonate, 3-chloro Dibenzylsulfonium salts such as -4-hydroxyphenyldibenzylsulfonium hexafluoroarsenate, 3-methyl-4-hydroxy-5-t-butylphenyldibenzylsulfonium hexafluoroantimonate;

4-hydroxyphenyl, 4-methoxybenzyl, methylsulfonium hexafluorophosphate, 4-hydroxyphenyl, 4-chlorobenzyl, methylsulfonium hexafluoroantimonate, 4-hydroxyphenyl, 4-nitrobenzyl, methylsulfonium hexafluoroantimonate, 4-hydroxyphenyl, 4-chlorobenzyl, methylsulfonium hexafluorophosphate, 3-methyl-4-hydroxyphenyl, 4-nitrobenzyl, methylsulfonium hexafluoroantimonate, 4-hydroxyphenyl, 3,5-dichlorobenzyl, methyl Sulfonium hexafluoroantimonate, 3-chloro-4-hydroxyphenyl, 2-chlorobenzyl, methylsulfonium hexafluoroantimonate DOO, and substituted benzyl sulfonium salts such as 4-hydroxyphenyl-benzyl-4-methoxybenzyl hexafluorophosphate can be exemplified.

  Specific examples of the benzothiazonium salt include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate, 3- Benzylbenzo such as (4-methoxybenzyl) benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazolium hexafluoroantimonate Mention may be made of thiazolium salts.

Of the sulfonium salts (1) and benzothiazolium salts, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, 4-hydroxyphenyl benzyl methylsulfonium hexafluoroantimonate, 4-acetoxyphenyl benzyl methylsulfonium hexamonate Fluoroantimonate, 4-hydroxyphenyl dibenzylsulfonium hexafluoroantimonate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate and the like are preferable. Commercial products of these compounds include Sun Aid SI-L85, SI-L110, SI-L145, SI-L150, SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.).
The said thermal acid generator can be used individually or in mixture of 2 or more types.

The acid crosslinking agent is represented by the following formula —CH ₂ OR ^4.
(In the formula, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6, preferably 1 to 4 carbon atoms.)
Is preferably a compound having two or more monovalent organic groups (hereinafter referred to as “methylol (ether) group”) in one molecule, and more preferably the monovalent organic group is a nitrogen atom. Ie, a compound having an N-methylol group and / or an N-alkoxymethyl group. When the acid crosslinking agent has two or more methylol (ether) groups in one molecule, each methylol (ether) group may be the same as or different from each other.

In the case where the acid crosslinking agent has (B) the binder resin has a carboxyl group, the methylol (ether) group in the acid crosslinking agent is in the presence of an acid generated from the thermal acid generator, and (B) the carboxyl in the binder resin. It is a component that reacts with a group to form a crosslinked structure.
As such an acid crosslinking agent, for example,
Alkoxymethylated melamines such as N, N, N, N, N, N-hexa (alkoxymethyl) melamine represented by the following formula (2);

[In Formula (2), R < ⁵ > -R < ¹⁰ > shows a C1-C6 alkyl group mutually independently normally, Preferably it is 1-4. ]
Alkoxymethylated glycolurils such as N, N, N, N-tetra (alkoxymethyl) glycoluril represented by the following formula (3),

[In Formula (3), R < ¹¹ > -R < ¹⁴ > shows a C1-C6 alkyl group mutually independently normally, Preferably it is 1-4. ]
And so on.

Examples of acid crosslinking agents other than the above include urea-formaldehyde resins, thiourea-formaldehyde resins, melamine-formaldehyde resins, guanamine-formaldehyde resins, benzoguanamine-formaldehyde resins, glycoluril-formaldehyde resins, polyvinylphenols, and the like. A compound having an ether group introduced therein can also be used.
These acid crosslinking agents can be used alone or in admixture of two or more.

  Of the acid crosslinking agents, alkoxymethylated melamines and alkoxymethylated glycolurils are preferable, and alkoxymethylated melamines are particularly preferable. In addition, the weight of alkoxymethylated melamines (α) and alkoxymethylated glycolurils (β) is excellent in weight because it has an excellent balance of crosslinkability, heat resistance and solvent resistance, and a cured product having a low dielectric constant can be obtained. As the ratio [(α) / (β)], an acid crosslinking agent mixed preferably at a ratio of 5/95 to 95/5, more preferably 10/90 to 90/10 can be used particularly preferably.

-Preparation method of resin composition for inkjet color filter-
The method for preparing the resin composition for an ink jet color filter of the present invention is not particularly limited, but a solvent having (A) a pigment, (B) a dispersant, and (C) two acetate structures in advance. It is preferable to prepare through a step of dispersing in a medium containing.
Hereinafter, the step of dispersing (A) the pigment in the medium in advance is referred to as “preliminary dispersion step”, and the dispersion in which (A) the pigment is dispersed in the medium in advance is referred to as “preliminary dispersion”.
The preliminary dispersion step can be carried out by mixing the above components using a mixing apparatus such as a dissolver, a bead mill, or a rod mill.
The average particle size of the (A) pigment in the preliminary dispersion thus obtained is preferably 50 to 400 nm, more preferably 50 to 150 nm.
Following the preliminary dispersion step, a preliminary dispersion, (D) a polyfunctional monomer and (E) a binder resin, and optionally (F) a photopolymerization initiator and a solvent are further added to the conventional method. By mixing by (3), the ink-jet color filter (radiation sensitive) composition of the present invention can be obtained.

Method for Forming Color Filter Next, a method for producing a color filter by the ink jet method in the present invention using the above resin composition for an ink jet type color filter (hereinafter simply referred to as “color filter production method”) will be described.
FIG. 2 is a longitudinal sectional view of a main part illustrating a liquid crystal display device having a color filter manufactured by the method for manufacturing a color filter in the present invention.
As shown in the figure, the color filter 1 basically includes a substrate 101, a partition wall 102, pixel patterns 20 (for example, red), 21 (for example, green) and 22 (for example, blue) for each color, and a protective layer 103 that covers the pixel pattern. These components are light-transmitting except for the partition wall 102, but the partition wall 102 may be light-transmitting or light-blocking.
Further, in the liquid crystal display device 6, the polarizing plate 201 is disposed on the outer surface side of the substrate 101, and the common electrode 202, the alignment film 203, the liquid crystal layer 204, the alignment film 205, the pixel electrode 206, the substrate are disposed on the protective layer 103. 207 and polarizing plate 208 are basically laminated.

As the material of the substrate 101, an appropriate light-transmitting material can be adopted as long as it has heat resistance against heating conditions in the color filter manufacturing process and has a mechanical strength of a certain level or more. Examples thereof include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, norbornene-based ring-opening polymer and hydrogenated products thereof. In addition, the substrate made of these materials may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. You can also.
These materials can also be used for the substrate 207, but the materials may be changed between the two substrates depending on circumstances.

The partition wall 102 is formed of a suitable resin composition for forming a partition wall, and the surface of the substrate 101 is partitioned in a lattice shape in the figure, and the region partitioned by the partition wall 102 has a light transmission region that transmits light. There is no. However, the partition shape by the partition 102 may be changed as desired.
Examples of the resin composition used for forming the partition wall 102 include (i) a radiation-sensitive resin composition that contains a binder resin, a polyfunctional monomer, a photopolymerization initiator, and the like and is cured by irradiation with radiation. And (ii) a binder resin, a compound that generates an acid upon irradiation with radiation, a crosslinkable compound that can be cross-linked with the action of an acid generated upon irradiation with radiation, and the like. Things can be used. These partition wall-forming radiation-sensitive resin compositions are usually prepared as a liquid composition by mixing a solvent when used, and this solvent may be a high-boiling solvent or a low-boiling solvent.

  Examples of the radiation-sensitive resin composition for forming partition walls in the present invention include (a) hexafluoropropylene, unsaturated carboxylic acid (anhydride), and other copolymers as described in JP-A No. 11-281815. A copolymer with a possible ethylenically unsaturated monomer, (b) a compound capable of generating an acid upon irradiation with radiation, (c) a crosslinkable compound capable of crosslinking by the action of an acid generated upon irradiation with radiation, (d A composition containing a fluorine-containing organic compound other than the component (a) and a solvent capable of dissolving the components (a) to (d) is preferable.

The pixel pattern 20 is formed from a color filter resin composition containing, for example, a red colorant, the pixel pattern 21 is formed from, for example, a color filter resin composition containing a green colorant, and the pixel pattern 22 is For example, it is formed from the resin composition for color filters containing a blue coloring agent, and these pixel patterns are formed by the inkjet system mentioned later.
The total number of pixel patterns defined by the partition walls 102 is obtained by multiplying the number of pixel patterns of each color in the liquid crystal display device by the number of primary colors (the three primary colors of red, green, and blue in the figure). For example, in the case of a VGA type liquid crystal display device used for an information terminal such as a personal computer, the number of pixel patterns for each color is 640 columns × 480 rows, so that a total of (640 × 480 × 3) pixel patterns are used. Will be composed. The arrangement pitch of the pixel pattern is, for example, 100 μm. In the figure, the number of pixel patterns is reduced to facilitate understanding.

The material of the protective layer 103 may be a normal material used for forming a protective layer for a color filter, but it can be used by a light or heat action or a light that can use a general-purpose exposure apparatus, a baking furnace or a hot plate. What is hardened | cured by combined use with a heat | fever is preferable, and it becomes possible to aim at the cost reduction of an installation, and space saving.
Further, the common electrode 202 can be formed by using a material having optical transparency and conductivity, for example, ITO (Indium Tin Oxide) and processing it by a conventional method.
The alignment films 203 and 205 can be formed, for example, by subjecting a film formed from an appropriate liquid crystal aligning agent to a rubbing process and the like, and have an action of aligning liquid crystal molecules in a certain direction.

The liquid crystal layer 204 is composed of polarized liquid crystal molecules, and is configured such that the orientation direction of the liquid crystal molecules can be controlled by applying a voltage.
The pixel electrode 206 is arranged corresponding to each pixel pattern of the color filter 1 and connected to the output terminal of the driving means (see FIG. 4). The pixel electrode 206 is also made of a material having optical transparency and conductivity, and the same material as that of the common electrode 202 can be used as the material. Good. As the driving means, for example, a TFT (Thin Film Transistor), a TFD (Thin Film Diode), or the like can be used.

  Polarizing plates 201 and 208 are attached to the outside of the substrates 101 and 207. These polarizing plates transmit only light in a specific polarization state out of backlight light irradiated from behind the liquid crystal display device 6. These two polarizing plates are arranged such that the polarization direction of light after passing through them is “deviated” by, for example, the polarization rotation angle given to the light by the liquid crystal molecules when no voltage is applied to the liquid crystal layer 204. .

Next, a manufacturing process of the color filter will be described with reference to FIGS.
Here, only the manufacturing process of the color filter 1 in the liquid crystal display device 6 will be described. A known technique can be applied to manufacture the remaining components of the liquid crystal display device 6.
FIG. 1 is a longitudinal sectional view of a main part illustrating the manufacturing process of the color filter 1, showing a cut surface corresponding to the AA arrow view of FIG. 3, and FIG. 3 is a plan view of the color filter 1. is there.
First, the partition wall forming radiation-sensitive resin composition is applied as a solution to the substrate 101 and then pre-baked (PB) to evaporate the solvent to form a coating film. The PB conditions in this case are, for example, a heating temperature of about 50 to 150 ° C. and a heating time of about 30 to 600 seconds.

Thereafter, this coating film is irradiated with radiation through a photomask and subjected to post-exposure baking (PEB), and then developed with an alkaline developer to dissolve and remove the unirradiated portions of the coating film. As a result, as shown in FIG. 1A, a plurality of light transmission regions 105 that transmit light on the surface of the substrate 101 are arranged on the surface of the substrate 101, in which partition patterns of a predetermined shape partitioned by the partition walls 102 are arranged according to a predetermined arrangement. A formed substrate is obtained. The PEB conditions in this case are, for example, a heating temperature of about 50 to 150 ° C., a heating time of about 30 to 600 seconds, and a radiation irradiation condition of, for example, about 1 to 500 mJ / cm ² . The developing condition is, for example, about 10 to 300 seconds. As the developing method, for example, a liquid piling method, a dipping method, a vibration dipping method, or the like can be employed. Further, post-baking may be performed after development, and the conditions are, for example, a heating temperature of about 150 to 280 ° C. and a heating time of about 3 minutes to 2 hours.

Next, as shown in FIG. 1 (b), the resin composition for an inkjet color filter is discharged from the inkjet head 10 to each light transmission region 105, and the upper surface of the resin composition is raised from the upper end of the partition wall 102. Are stored in the respective light transmission regions 105 so as to form the storage layers 21, 22,... Of the resin composition. In addition, 20 has illustrated the state in the middle of discharge of a resin composition. In this case, the discharge speed of the resin composition is, for example, about 0.01 to 100 m / second.
Thereafter, as shown in FIG. 1C, the resin composition forming each reservoir layer is subjected to a heat treatment to evaporate the solvent, thereby drying the resin composition, and the pixel patterns 20 and 21 having a predetermined thickness. , 22,... Note that the volume of each reservoir is reduced by such processing. The heat treatment in this case is performed using, for example, a heater, and is performed by heating the whole to a predetermined temperature (for example, about 50 ° C.).

Thereafter, in some cases, after irradiation with radiation, in order to completely dry and crosslink the resin composition, heating at a predetermined temperature (for example, about 150 to 280 ° C.) for a predetermined time (for example, about 3 minutes to 2 hours) is performed. Do. In this case, the radiation irradiation condition is, for example, about 1 to 500 mJ / cm ² .
When forming the pixel patterns 20, 21, 22,..., A red, green, or blue resin composition is sequentially used, for example, so that a pixel array of the three primary colors red, green, and blue is disposed on the substrate 101. be able to.

Thereafter, as shown in FIG. 1D, a protective layer 103 is formed by using an appropriate resin so as to cover the formed pixel patterns and to flatten the surface of the color filter.
Further, the common electrode 202 is formed on the protective layer 103 by using a material having light permeability and conductivity (for example, ITO) by a method such as sputtering or vapor deposition. In the case of forming a pattern on the common electrode 202, the common electrode 202 is etched in accordance with the pattern shape of other components such as the pixel electrode 206.
The color filter 1 can be manufactured through the above steps.

Next, as shown in FIG. 1E, an alignment film 203, a liquid crystal layer 204, and an alignment film 205 are sequentially formed between the color filter 1 and the substrate 207 on which the pixel electrode 206 is separately disposed, and both outer surfaces thereof are formed. Then, the polarizing plates 201 and 208 are attached to the liquid crystal display device 6.
When the partition wall forming radiation-sensitive resin composition is applied to the substrate 101, an appropriate application method such as spin coating, cast coating, roll coating, or the like can be employed. The coating thickness is usually 0.1 to 10 μm, preferably 0.5 to 3.0 μm, as the film thickness after PB.

As the radiation used when forming the partition wall 102 and the pixel patterns 20, 21, 22,..., Visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, and the like can be used. Radiation in the range of 190-450 nm is preferred.
Examples of the alkaline developer used for forming the partition wall 102 include sodium carbonate, sodium hydroxide, potassium hydroxide, sodium silicon, sodium metasilicon, ammonia water, ethylamine, n-propylamine, diethylamine, Di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0]- An aqueous solution such as 7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonene is preferable.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, after development with an alkaline developer, it is usually washed with water.

Next, FIG. 4 illustrates an outline of a color filter manufacturing apparatus used in the color filter manufacturing method of the present invention.
The color filter manufacturing apparatus includes a control device 2 that controls the inkjet head 10, motors 3 and 4, a position sensor 5, and the like.
The inkjet head 10 is for discharging the supplied resin composition for a color filter from its nozzle, and its form is not particularly limited, and a known inkjet method may be used, but in the present invention, the color filter Since the resin composition for use is used, a piezo jet type resin that does not cause heat to act on the resin composition is preferable so as not to damage the material.
The piezoelectric jet type inkjet head 10 is provided with N piezoelectric elements 40 (N is an arbitrary number) for discharging the color filter resin composition. Further, the piezoelectric element 40 is configured so that driving and non-driving can be individually controlled.

FIG. 5 illustrates a partially cutaway view of the main part of the inkjet head 10.
The ink jet head 10 mainly includes a pressure chamber substrate 11, a vibration plate 12 and a nozzle plate 13, and the vibration plate 12 is provided on one surface of the pressure chamber substrate 11. Provided on the other surface.
The pressure chamber substrate 11 is formed with a pressure chamber 14, a side wall 15, a reservoir 16, a supply port 17, and the like by etching a silicon substrate, for example, and volume change occurs in the pressure chamber 14 due to deformation of the diaphragm 12. As described above, the piezoelectric elements 40 provided on the diaphragm 12 and the pressure chambers 14 are aligned.

The diaphragm 12 is an elastic film made of ceramics or the like, and is provided with the piezoelectric elements 40 arranged so as to be deformed by the distortion of the piezoelectric elements 40. The diaphragm 12 is provided with an ink tank port 18 so that a color filter resin composition stored in an ink tank (not shown) can be supplied into the pressure chamber substrate 11. The color filter resin composition thus made flows through the path of the reservoir 16 → each supply port 17 → each pressure chamber 14. The piezoelectric element 40 is configured by sandwiching a piezoelectric ceramic crystal between electrodes.
The nozzle plate 13 is provided with nozzles 19 for discharging the resin composition for color filters, and each nozzle 19 corresponds to each pressure chamber 16.
The ink jet heads 10 are provided only for the types of resin compositions for color filters, and actually, for example, the red, green and blue ink jet heads 10 are used. However, only one inkjet head 10 is shown here for easy understanding.

  In such an ink jet head 10, only the piezoelectric element 40 to which a voltage is applied to the drive circuit is distorted, the diaphragm 12 is deformed, and pressure is applied to the pressure chamber 14 corresponding to the piezoelectric element. The resin composition for a color filter is discharged from the nozzle 19. Since the piezoelectric element 40 to which no voltage is applied is not distorted, the resin composition in the corresponding pressure chamber 14 is not discharged. Therefore, one set of the piezoelectric element 40, the pressure chamber 14, and the nozzle 19 constitutes one operating unit.

Further, FIG. 6 illustrates a plan view of the filter elements on the substrate 101 on which the nozzles 19 in the inkjet head 10 are arranged and the partition wall 102 on which the color filter 1 is formed.
Assuming that N nozzle numbers are hn (n is a number from 1 to N), the position Nn (xn, yn) of each nozzle 19 is specified by the relative coordinate x2 axis and the y2 axis as shown in the figure. It is like that.
The smallest pixel element partitioned by the grid of the partition wall 102 is called a filter element, and for example, a window having a width of about 300 μm in the x1 axis (horizontal) direction and a length of about 100 μm in the y1 axis (vertical) direction is formed. In the substrate on which the partition wall is formed, the position Wm (xm, ym) of each filter element (m is a number from 1 to the maximum number of filter elements) is specified by the relative coordinate x1 axis and the y1 axis. ing.

  The pitch of each nozzle 19 is set to an integral multiple of the pitch in the x1 axis direction. For example, in the case where 60 nozzles 19 are arranged in the inkjet head 10 and three drops of the color filter resin composition are ejected to one filter element, when the inkjet head 10 is operated at a driving frequency of 14.4 kHz, about 900,000 pixels In the 10 type VGA color filter, the resin composition can be stored at 900,000 pixels × 3 drops / (14400 times / second × 60) = about 3 seconds. However, since it is necessary to consider the moving time of the inkjet head 10, the resin composition can be actually stored in all the filter elements within one minute.

Such a method for producing a color filter is very advantageous industrially because the production process is simple and the cost is low. In addition, in the present invention, as described above, the pixel pattern forming operation is extremely industrially advantageous by using the resin composition for an ink-jet color filter containing a high boiling point solvent.
The color filter manufactured by the above-described color filter manufacturing method is extremely useful as, for example, a color liquid crystal display device, a color image pickup tube element, and a color sensor as an additive color mixing type and a subtractive color mixing type.

Color Filter The color filter of the present invention is characterized by having a pixel pattern formed by an inkjet method using the resin composition for an inkjet color filter of the present invention.
The color filter of the present invention is extremely useful for color imaging tube elements, color sensors, etc., in addition to transmissive or reflective color liquid crystal display devices.

Liquid crystal display device The liquid crystal display device of the present invention comprises the color filter of the present invention.
The liquid crystal display device of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other through the liquid crystal layer. Further, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed include a liquid crystal layer. It is also possible to adopt a structure facing each other. The latter structure has the advantage that the aperture ratio can be remarkably improved and a bright and high-definition liquid crystal display device can be obtained.
[Other Embodiments According to the Present Invention]
Other aspects of the present invention include the following.
A pigment dispersion composition comprising (A) a pigment, (B) a dispersant, and (C) a solvent having two acetate structures.
Further, it comprises (A) a pigment, (B) a dispersant, (C) a solvent having two acetate structures, (D) a polyfunctional monomer, and (E) a binder resin. It is a resin composition for inkjet color filters.
(A) a pigment, (B) a dispersant, (C) a solvent having two acetate structures, (D) a polyfunctional monomer, (E) a binder resin, and (F) a photopolymerization initiator. A radiation-sensitive resin composition for an ink-jet color filter.
Moreover, it is a color filter characterized by having the pixel pattern formed by the inkjet system using the said ink-jet color filter (radiation sensitive) resin composition.
In addition, a liquid crystal display device including the color filter is provided.

  Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Example 1
(A) CI Pigment Red 254 / CI Pigment Red 177 = 92/8 (weight ratio) mixture 15 parts by weight as a pigment, (B) Disperbyk-2000 (solid content concentration 46.2% by weight) 5 parts by weight as a dispersant ( About 2.31 parts by weight in terms of solid content) and 40 parts by weight of 1,3-butylene glycol diacetate as (C), and 40 parts by weight of propylene glycol monomethyl ether acetate as other solvent. R1) was prepared.
Next, 100 parts by weight of the preliminary dispersion (R1), (E) methacrylic acid / succinic acid mono (2-methacryloyloxyethyl) / N-phenylmaleimide / styrene / benzyl methacrylate copolymer (copolymerization weight ratio) as a binder resin = 25/10/30/20/15, Mw = 12,000, Mn = 6,500) 5 parts by weight, (D) 10 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (F) light 5 parts by weight of 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propanone-1 as a polymerization initiator and 70 parts by weight of 1,3-butylene glycol diacetate as (C) were mixed, A resin composition was prepared.

Example 2
(A) CI Pigment Green 36 / CI Pigment Yellow 150 = 47.5 / 52.5 (weight ratio) 15 parts by weight as a pigment, (B) 7 parts by weight of Disperbyk-2000 as a dispersant (approximately 3 in terms of solid content) .465 parts by weight) and 39 parts by weight of 1,3-butylene glycol diacetate as (C) and 39 parts by weight of propylene glycol monomethyl ether acetate as another solvent in the same manner as in Example 1, G1) was prepared.
Next, 100 parts by weight of the preliminary dispersion (G1), (E) a methacrylic acid / N-phenylmaleimide / styrene / benzyl methacrylate / glycerol monomethacrylate copolymer (copolymerization weight ratio = 15/25/15/35) as a binder resin / 10, Mw = 1,500, Mn = 6,000) 5 parts by weight, (D) 10 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (F) 2-benzyl- as a photopolymerization initiator A resin composition was prepared by mixing 5 parts by weight of 2-dimethylamino-1- (4-morpholinophenyl) butanone-1 and 70 parts by weight of 1,3-butylene glycol diacetate as (C).

Example 3
(A) CI Pigment Blue 15: 6 / CI Pigment Violet 23 = 80/20 (weight ratio) 15 parts by weight as a pigment, (B) 9 parts by weight of Disperbyk-2000 as a dispersant (4.62 wt in terms of solid content) Part) and 38 parts by weight of 1,3-butylene glycol diacetate as (C) and 38 parts by weight of propylene glycol monomethyl ether acetate as the other solvent in the same manner as in Example 1 to prepare the preliminary dispersion (B1). Prepared.
Next, 100 parts by weight of the preliminary dispersion (B1), (E) methacrylic acid / N-phenylmaleimide / α-methylstyrene / benzyl methacrylate (copolymerization weight ratio = 20/25/25/30, Mw = 43 as binder resin) , 1,000, Mn = 21,000) 10 parts by weight, (D) 20 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (F) 2-methyl- (4-methylthiophenyl) as a photopolymerization initiator A resin composition was prepared by mixing 5 parts by weight of 2-morpholino-1-propanone-1 and 110 parts by weight of 1,3-butylene glycol diacetate as (C).

Example 4
In the preliminary dispersion step in Example 1, 40 parts by weight of 1,3-butylene glycol diacetate as (C) and 40 parts by weight of propylene glycol monomethyl ether acetate as the other solvent, but propylene glycol monomethyl ether acetate as the other solvent A resin composition was prepared in the same manner as in Example 1 except that 80 parts by weight of the preliminary dispersion (R2) was prepared.

Example 5
(A) CI Pigment Red 254 / CI Pigment Red 177 = 92/8 (weight ratio) mixture 15 parts by weight as a pigment, (B) Disperbyk-2000 (solid content concentration 46.2% by weight) 5 parts by weight as a dispersant ( About 2.31 parts by weight in terms of solid content) and 40 parts by weight of 1,3-butylene glycol diacetate as (C), and 40 parts by weight of propylene glycol monomethyl ether acetate as other solvent. R1) was prepared.
Next, 100 parts by weight of the preliminary dispersion (R1), (E) methacrylic acid / succinic acid mono (2-methacryloyloxyethyl) / N-phenylmaleimide / styrene / benzyl methacrylate copolymer (copolymerization weight ratio) as a binder resin = 25/10/30/20/15, Mw = 12,000, Mn = 6,500) 5 parts by weight, (D) 10 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (C) As a mixture, 70 parts by weight of 1,3-butylene glycol diacetate was mixed to prepare a resin composition.

Comparative Example 1
In the preliminary dispersion step in Example 1, (C) is replaced with 40 parts by weight of 1,3-butylene glycol diacetate, and 40 parts by weight of diethylene glycol monobutyl ether acetate is used as another solvent to prepare a preliminary dispersion (r1). A resin composition was prepared in the same manner as in Example 1, except that 70 parts by weight of diethylene glycol monobutyl ether acetate was used as the other solvent in place of 70 parts by weight of 1,3-butylene glycol diacetate as C).

Comparative Example 2
In the preliminary dispersion step in Example 2, a preliminary dispersion (g1) was prepared using 39 parts by weight of diethylene glycol monobutyl ether acetate as the other solvent in place of 39 parts by weight of 1,3-butylene glycol diacetate as (C), ( A resin composition was prepared in the same manner as in Example 2 except that 70 parts by weight of diethylene glycol monobutyl ether acetate was used as the other solvent in place of 70 parts by weight of 1,3-butylene glycol diacetate as C).

Comparative Example 3
In the preliminary dispersion step in Example 3, a preliminary dispersion liquid (b1) was prepared using 38 parts by weight of diethylene glycol monobutyl ether acetate as the other solvent instead of 38 parts by weight of 1,3-butylene glycol diacetate as (C), ( A resin composition was prepared in the same manner as in Example 3, except that 70 parts by weight of diethylene glycol monobutyl ether acetate was used as the other solvent in place of 70 parts by weight of 1,3-butylene glycol diacetate as C).

Comparative Example 4
In the preliminary dispersion step in Example 1, 40 parts by weight of 1,3-butylene glycol diacetate as (C) and 40 parts by weight of propylene glycol monomethyl ether acetate as the other solvent, but propylene glycol monomethyl ether acetate as the other solvent A preliminary dispersion (R2) was prepared using 80 parts by weight, and instead of 70 parts by weight of 1,3-butylene glycol diacetate as (C), 70 parts by weight of propylene glycol monomethyl ether acetate was used as another solvent. A resin composition was prepared in the same manner as in Example 1.

Comparative Example 5
In the preliminary dispersion step in Example 1, 40 parts by weight of 1,3-butylene glycol diacetate as (C) and 40 parts by weight of propylene glycol monomethyl ether acetate as the other solvent, but propylene glycol monomethyl ether acetate as the other solvent A preliminary dispersion (R2) was prepared using 80 parts by weight, and instead of 70 parts by weight of 1,3-butylene glycol diacetate as (C), 70 parts by weight of diethylene glycol monobutyl ether acetate was used as another solvent, A resin composition was prepared in the same manner as in Example 1.

The preliminary dispersions and resin compositions obtained in each Example and each Comparative Example were evaluated in the following manner. The evaluation results are shown in Table 1 (Examples) and Table 2 (Comparative Examples).
Initial viscosity evaluation Initial viscosity was measured using an E-type viscometer. The required viscosity as a preliminary dispersion is 30 mPa.s. s or less, the required viscosity as the resin composition is 10 mPa.s. s or less, the resin compositions of the preliminary dispersions r1, g1, b1, and Comparative Examples 1, 2, and 3 were several hundred mPa.s. s and the required viscosity were exceeded.
Rheology evaluation It measured using the viscoelasticity measuring apparatus. At that time, when the complex viscosity at the strain rate of 10 s ⁻¹ is 1, the change rate of the value of the complex viscosity at the strain rate of 500 s ⁻¹ is required to be 20% or less. The resin compositions of r1, g1, b1, and Comparative Examples 1, 2, and 3 did not satisfy the required values.

Evaluation of storage stability:
Each preliminary dispersion and 50 g of the resin composition were put in a light-shielding glass container and allowed to stand at 40 ° C. for 1 week in a sealed state, and then the viscosity was measured using an E-type viscometer. At this time, the rate of change of the viscosity after standing with respect to the initial viscosity is calculated, and the rate of change is required to be 5% or less, but the preliminary dispersions r1, g1, and b1, the resins of Comparative Examples 1, 2, and 3 The composition did not meet the required value.
Sedimentation evaluation 50 g of each resin composition was put in a light-shielding glass container and allowed to stand at 23 ° C. for 3 months in a sealed state, and then the occurrence of sediment in the container was visually evaluated. The thing which did not generate | occur | produce was set to "(circle)", and the thing which generate | occur | produced was set to "x". It became "x" with the resin composition of Comparative Examples 1, 2, 3, and 5.

Inkjet Ejection Evaluation Using an inkjet ejection apparatus, the drop landing resilience, continuous ejection properties, and intermittent ejection properties when each resin composition was ejected were evaluated. “◯” indicates that there was no problem in all the evaluations of the landing elasticity, continuous discharge property, and intermittent discharge property, and “X” indicates that there was a problem in any of the evaluations. It became "x" with the resin composition of Comparative Examples 1, 2, 3, and 4.
Contrast evaluation About each resin composition, after film-forming on a glass substrate so that it might become a film thickness of 1.0 micrometer, (1) what has photosensitivity is prebaked at 80 degreeC for 10 minutes, and UV irradiation amount is 200 mJ / cm < ² >. After exposure, it was baked at 220 ° C. for 30 minutes, and (2) non-photosensitive material was pre-baked at 80 ° C. for 10 minutes and then baked at 220 ° C. for 30 minutes, and then the contrast was evaluated with a contrast measuring device. . When the contrast value was required to be 1,000 or more, the resin composition of Comparative Examples 1, 2, and 3 did not satisfy the required value.

The resin composition for an ink jet color filter of the present invention has good dispersion stability, is difficult to dry, and has excellent ink ejection properties. Therefore, the ink composition for a color filter when producing a color filter by the ink jet method is used. Useful.

1 color filter 2 control device 3 motor 4 motor 5 position sensor 6 liquid crystal display device 10 ink jet head 11 pressure chamber substrate 12 diaphragm 13 nozzle plate 14 pressure chamber 15 side wall 16 reservoir 17 supply port 18 ink tank port 19 nozzle 20 pixel pattern ( Red)
21 pixel pattern (green)
22 pixel pattern (blue)
40 piezoelectric element 101 substrate 102 partition 103 protective layer 105 light transmission region 201 polarizing plate 202 common electrode 203 alignment film 204 liquid crystal layer 205 alignment film 206 pixel electrode 207 substrate 208 polarizing plate

Claims (4)

  (A) a pigment, (B) a dispersant, (C) a solvent having two acetate structures, (D) a polyfunctional monomer, and (E) a binder resin, A resin composition for an ink-jet color filter, wherein the proportion of the solvent having two is 46 to 100% by weight with respect to the total solvent.   The resin composition for an ink jet type color filter according to claim 1, wherein a use ratio of the solvent having two (C) acetate structures is 73 to 100% by weight based on the whole solvent.   A color filter comprising a pixel pattern formed by an inkjet method using the resin composition for an inkjet color filter according to claim 1.   A liquid crystal display device comprising the color filter according to claim 3.

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