JP2006047686A - Radiation-sensitive composition for color filter, its preparation method, color filter and color liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive composition for a color filter with which a red pixel having high transmittance and a contrast ratio can be formed, the composition having rheological characteristics suitable for coating a large substrate. <P>SOLUTION: The radiation-sensitive composition contains: (A) a pigment; (B) a dispersant; (C) a copolymer of (c1) a carboxyl group-containing unsaturated monomer comprising an (meth)acrylic acid, (c2) N-site substituted maleimide, and (c3) at least one kind of copolymerizable unsaturated monomer selected from a group consisting of polystyrene macromonomers and polymethylmethacrylate macromonomers; (D) a polyfunctional monomer; (E) a radiation-sensitive radical generating agent; and (f) a solvent. The pigment (A) contains C.I.Pigment Red 242 by ≥20 wt.% and the average particle size r (nm) of the pigment (A) is in the range of 50≤r≤200. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a radiation sensitive composition for a color filter, a method for preparing the same, a color filter, and a color liquid crystal display device. More specifically, a radiation sensitive composition for a color filter useful for the production of a color filter used in a transmissive or reflective color liquid crystal device, a color image pickup tube element, etc., a preparation method thereof, and the radiation sensitive composition for the color filter The present invention relates to a color filter having red pixels formed from an object, and a color liquid crystal display device including the color filter.

As a method of forming a color filter using a colored radiation-sensitive composition, a coating film of a colored radiation-sensitive composition is formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed in advance. Radiation is irradiated through a mask having a pattern shape (hereinafter referred to as “exposure”), developed with an alkali developer to dissolve and remove unexposed portions, and then post-baked using a clean oven or hot plate. Thus, a method for obtaining pixels of each color is known (see Patent Document 1 and Patent Document 2).
A liquid crystal display device having such a color filter is required to have high luminance, and therefore, the color filter has recently been required to have a higher light transmittance. In response to such a requirement, as disclosed in Patent Document 3, C.I. I. Pigment red 254 and C.I. I. It is known that the combination of Pigment Red 242 is effective.

In recent years, with the spread of digital video cameras, high-definition televisions, and the like, there is an increasing demand for a high color density that can display a deep blue or bright sunset like a winter sea on a color liquid crystal display element. In order to display such a high color density, if the “blackness” of the black display portion is not clearly displayed, the screen has a sharp outline and no sharpness. Therefore, there is a need for a pixel or colored layer having a high contrast ratio.
Furthermore, with the increase in size of the liquid crystal display element, the size of the glass substrate at the time of manufacturing the color filter is also increasing. It is known that when the substrate becomes large, it becomes difficult to uniformly coat the entire surface of the substrate. As a typical application method of the radiation sensitive composition for color filters, there are a central dropping method, a slit & spin method, and a slit method. Is known to be greatly involved. In the coating performance, the desirable rheology of the liquid is a Newtonian liquid, but when the dispersion performance in the pigment dispersion system is poor, etc., it tends to be a non-Newtonian liquid. In that case, coating methods that rotate and control the film thickness, such as the central dropping method and the slit & spin method, show a difference in film thickness between the center and the outside of the substrate. As a result, it becomes a cause of coating defects such as film thickness non-uniformity and streak unevenness. Therefore, there is a demand for a radiation sensitive composition for color filters having rheological properties closer to that of a Newtonian liquid.
JP-A-2-144502 JP-A-3-53201 JP 2002-372618 A

An object of the present invention is to provide a radiation-sensitive composition for a color filter that can form a red pixel having a high light transmittance and a high contrast ratio and has rheological characteristics suitable for coating a large substrate.
Another object of the present invention is to provide a radiation sensitive composition for a color filter of the present invention.
Still another object of the present invention is to provide a color filter and a color liquid crystal display device having the color filter in connection with the radiation sensitive composition for a color filter of the present invention.
Still other objects and advantages of the present invention will become apparent from the following description.

The above objects and advantages of the present invention include, firstly, a carboxyl group-containing unsaturated monomer comprising (A) a pigment, (B) a dispersant, (C) (c1) (meth) acrylic acid, (C2) N-position substituted maleimide, (c3) styrene, α-methylstyrene, p-hydroxy-α-methylstyrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, A copolymer with at least one other copolymerizable unsaturated monomer selected from the group consisting of benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer, (D A radiation-sensitive composition comprising a) a multifunctional monomer, (E) a radiation-sensitive radical generator, and (F) a solvent, A) The pigment is C.I. I. It is achieved by a radiation sensitive composition for a color filter, comprising 20% by weight or more of Pigment Red 242 and (A) an average particle diameter r (unit: nm) of the pigment is 50 ≦ r ≦ 200.
The “radiation” as used in the present invention means a substance including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.

  The above objects and advantages of the present invention are, secondly, C.I. I. Pigment Red 242 is contained in an amount of 20% by weight or more, and the average particle size exceeds 200 nm. (A) Pigment, (B) Dispersant, (C) At least part of copolymer and (F) At least part of solvent. Dispersed in a medium, and then the obtained dispersion is (D) a polyfunctional monomer, (E) a radiation-sensitive radical generator, and (C) a copolymer and (F) a solvent as required. It is achieved by the method for preparing the radiation sensitive composition for a color filter, which comprises mixing.

  Thirdly, the above objects and advantages of the present invention are achieved by a color filter having a red pixel formed from the radiation sensitive composition for a color filter.

  Fourth, the above objects and advantages of the present invention are achieved by a color liquid crystal display device comprising the color filter.

The radiation sensitive composition for a color filter of the present invention has rheological characteristics suitable for coating a large substrate, and can form red pixels having a high light transmittance and a high contrast ratio.
Therefore, the radiation sensitive composition for color filters of the present invention can be used very suitably for the formation of various color filters including color filters for color liquid crystal display devices in the electronic industry.

Hereinafter, the present invention will be described in detail.
(A) Pigment The pigment in the present invention is C.I. in the color index (CI; issued by The Society of Dyers and Colorists, the same applies hereinafter). I. Pigment Red 242 is included.
The pigment in the present invention may further contain other pigments as the case may be.
The other pigment is not particularly limited, but an organic pigment is preferable because the color filter is required to have high purity and highly transparent coloring and heat resistance.
Examples of the other organic pigments include compounds classified as pigments in the color index, specifically, those having the following color index (CI) numbers.

  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 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 51, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74,

C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 9, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 208, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 215, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment Red 272.

Among these other organic pigments, C.I. I. Pigment yellow 139, C.I. I. Pigment orange 38, C.I. I. Pigment red 177 and C.I. I. At least one selected from the group consisting of CI Pigment Red 254 is preferable. I. Pigment Red 254 is particularly preferred.
The other organic pigments can be used alone or in admixture of two or more.
The pigment C.I. I. The content of Pigment Red 242 is 20% by weight or more, that is, 20 to 100% by weight, preferably 30 to 100% by weight, and particularly preferably 50 to 100% by weight. By using such a pigment, a red pixel having a high contrast ratio and a high transmittance can be obtained, and a radiation sensitive composition for a color filter having rheological properties suitable for coating on a large substrate can be obtained. Can do.
In the present invention, C.I. I. Pigment Red 242 and other pigments can be used after purification by recrystallization method, reprecipitation method, solvent washing method, sublimation method, vacuum heating method, a combination thereof, or the like, if necessary.

The average particle diameter r (unit: nm) of the pigment used in the present invention should satisfy 50 ≦ r ≦ 200, preferably 50 ≦ r ≦ 150. By using such a pigment having an average particle diameter r, a red pixel having a high contrast ratio and a high transmittance can be obtained. The “average particle diameter” as used herein means the average particle diameter of secondary particles in which primary particles (single microcrystals) of the pigment are aggregated.
The particle size distribution of the secondary particles of the pigment used in the present invention (hereinafter simply referred to as “particle size distribution”) is preferably such that the secondary particles falling within (average particle size ± 100) nm are It is desirable that it is 70% by weight or more, more preferably 80% by weight or more.
Pigments having the above average particle size and particle size distribution are commercially available C.I. I. Pigment Red 242 (average particle size is typically greater than 300 nm), along with other optional pigments (average particle size is typically greater than 300 nm), together with (B) dispersant, (C) alkali soluble The pigment mixture mixed with the resin and the solvent can be prepared, for example, by mixing and dispersing while pulverizing using a pulverizer such as a bead mill or a roll mill. The pigment thus obtained is usually in the form of a pigment dispersion.

(B) Dispersant The dispersant in the present invention is, for example, polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxy Polyoxyethylene alkyl phenyl ethers such as ethylene n-nonyl phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid modified polyesters; tertiary amine modified polyurethanes; polyethylene imines, The following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and F-Top (manufactured by Tochem Products). , Megafuck (Dainippon Ink Chemical Co., Ltd.), Florard (Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Disperbyk-101, -103, and- 107, -110, -111, -115, -130, -160, -160, -161, -162, -163, -164, -165, -166, -170, -180, -182, -2000, -2001 (above, manufactured by Big Chemie Japan Co., Ltd.), Solsperse S5000, 12000, 13240, 13940, 17000, 20000, 22000, 24000 , 24000GR, 26000, 27000, 28000 (above, manufactured by Avicia Co., Ltd.), EFKA46, 47, 48, 745, 4540, 4550, 6750, EFKA LP4008, 4009, 4010, 4015, 4050, 4055, 4560, 4800, EFKA Polymer400, 401, 402, 403, 450, Examples 451 and 453 (manufactured by Fuka Chemicals Co., Ltd.); Ajispa-PB-821 and 822 (manufactured by Ajinomoto Fine Techno Co., Ltd.), and the like.
These dispersants can be used alone or in admixture of two or more.

The amount of the dispersant used (in terms of solid content) in the present invention is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, based on 100 parts by weight of the (A) pigment. In this case, if the amount of the dispersant used is less than 1 part by weight, the storage stability of the resulting composition tends to decrease, whereas if it exceeds 50 parts by weight, a residue tends to be generated on the substrate. .
Moreover, as a solvent used when preparing a pigment dispersion liquid, the thing similar to the solvent mentioned later about the radiation sensitive composition for color filters in this invention can be mentioned, for example.
The amount of the solvent used in preparing the pigment dispersion is preferably 500 to 1,000 parts by weight, more 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 the pigment mixture is preferably mixed while cooling with cooling water or the like. It can be implemented by dispersing.
In this case, the filling rate of beads is preferably 50 to 80% of the mill capacity, and the injection amount of the pigment mixture is preferably about 20 to 50% of the mill capacity. The treatment time is preferably 2 to 50 hours, more preferably 2 to 25 hours.
Moreover, when preparing a pigment dispersion using a roll mill, for example, a three-roll mill or a two-roll mill is used, and the pigment mixture is preferably treated while being cooled with cooling water or the like. be able to.
In this case, the roll interval is preferably 10 μm or less, and the shearing force is preferably about 10 ⁸ dyn / second. The treatment time is preferably 2 to 50 hours, more preferably 2 to 25 hours.
The average particle size and particle size distribution of the pigment in the pigment dispersion thus prepared can be measured by a dynamic light scattering method.

(C) Copolymer (alkali-soluble resin)
As the copolymer (alkali-soluble resin) in the present invention, (A) a developer that acts as a binder for the pigment and that is used in a development step when producing a color filter, particularly preferably an alkali developer. Although it is not particularly limited, an alkali-soluble resin having a carboxyl group is preferable. In particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “carboxyl group”). Containing unsaturated monomer ”) and other copolymerizable ethylenically unsaturated monomer (hereinafter referred to as“ copolymerizable unsaturated monomer ”) (hereinafter referred to as“ carboxyl ”). Group-containing copolymer ").

As the carboxyl group-containing unsaturated monomer, for example,
Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or anhydrides thereof;
A trivalent or higher unsaturated polycarboxylic acid or anhydride thereof;
Mono [(meth) acryloyloxyalkyl] of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ester;
Examples thereof include mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate.
Among these carboxyl group-containing unsaturated monomers, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are respectively M-5300 and M-5400 (Toagosei ( (Commercially available) under the trade name.
The said carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.

Examples of the copolymerizable unsaturated monomer include:
Maleimide;
N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimidobenzoate, N- N-substituted maleimides such as succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (acridinyl) maleimide;
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, p-hydroxy-α-methylstyrene Aromatic vinyl compounds such as o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether;
Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate Rate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl Such as (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate Saturated carboxylic acid esters;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethyl Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Other unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These copolymerizable unsaturated monomers can be used alone or in combination of two or more.

  The carboxyl group-containing copolymer in the present invention preferably comprises (c1) (meth) acrylic acid as an essential component, and optionally succinic acid mono [2- (meth) acryloyloxyethyl] and / or ω-carboxypolycarbonate. Carboxyl group-containing unsaturated monomer containing chlorolactone mono (meth) acrylate, (c2) N-substituted maleimide, (c3) styrene, α-methylstyrene, p-hydroxy-α-methylstyrene, methyl Other selected from the group consisting of (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer Less copolymerizable unsaturated monomer Copolymer also one (hereinafter, "carboxyl group-containing copolymer (C1)" hereinafter.) Is.

As preferable specific examples of the carboxyl group-containing copolymer (C1),
(Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / Nm-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / Np-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-cyclohexylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / α-methylstyrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / p-hydroxy-α-methylstyrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / Np-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / phenyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / phenyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / Np-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / allyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / allyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycacrolactone mono (meth) acrylate / Nm-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycacrolactone mono (meth) acrylate / Np-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycacrolactone mono (meth) acrylate / N-phenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
Examples thereof include (meth) acrylic acid / ω-carboxypolycacrolactone mono (meth) acrylate / Np-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer.

Moreover, as a carboxyl group-containing copolymer other than the carboxyl group-containing copolymer (C1), for example,
(Meth) acrylic acid / methyl (meth) acrylate copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer and the like.

  In the carboxyl group-containing copolymer, the copolymerization ratio of the carboxyl group-containing unsaturated monomer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. In this case, when the copolymerization ratio is less than 5% by weight, the solubility of the resulting radiation-sensitive composition in an alkali developer tends to be reduced, whereas when it exceeds 50% by weight, the solubility in an alkali developer is low. When the development is performed with an alkaline developer, the pixel tends to drop off from the substrate or the surface of the pixel becomes rough.

  In the carboxyl group-containing copolymer (C1), the copolymerization ratio of the carboxyl group-containing unsaturated monomer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. In this case, if the copolymerization ratio of the carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility of the resulting radiation-sensitive composition in an alkaline developer tends to decrease, whereas if it exceeds 50% by weight. In addition, the solubility in an alkali developer tends to be excessive, and the pixel tends to drop off from the substrate when developing with an alkali developer.

The copolymerization ratio of the N-substituted maleimide is preferably 5 to 40% by weight, more preferably 10 to 30% by weight. In this case, if the copolymerization ratio of the N-substituted maleimide is less than 5% by weight, a residue tends to be generated during development, whereas if it exceeds 40% by weight, the adhesion of the pixel to the substrate tends to decrease. There is.
Furthermore, the copolymerization ratio of the other copolymerizable unsaturated monomer is preferably 30 to 90% by weight, more preferably 40 to 80% by weight. In this case, when the copolymerization ratio of the other copolymerizable unsaturated monomer is less than 30% by weight, the adhesion of the pixel to the substrate tends to be lowered. There is a tendency for solubility to decrease.

Mw measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of an alkali-soluble resin is preferably 3,000 to 300,000, more preferably 5,000 to 100,000.
Moreover, Mn measured by the gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of alkali-soluble resin becomes like this. Preferably it is 3,000-60,000, More preferably, it is 5,000-25,000.
Moreover, the ratio (Mw / Mn) of Mw and Mn of the alkali-soluble resin is preferably 1 to 5, more preferably 1 to 4.

In the present invention, by using such an alkali-soluble resin having specific Mw and Mn, a radiation-sensitive composition having excellent developability can be obtained, and thereby a pixel pattern having sharp pattern edges can be obtained. In addition to being able to be formed, residues, background stains, film residues and the like are less likely to occur on the unexposed substrate and the light shielding layer during development.
In this invention, alkali-soluble resin can be used individually or in mixture of 2 or more types.

  The amount of the alkali-soluble resin used in the present invention is preferably 10 to 1,000 parts by weight, more preferably 20 to 500 parts by weight with respect to 100 parts by weight of the (A) pigment. In this case, if the amount of the alkali-soluble resin used is less than 10 parts by weight, for example, the alkali developability may decrease, or background stains or film residues may occur on the substrate or the light shielding layer in the unexposed area. When the amount exceeds 1,000 parts by weight, the pigment concentration is relatively lowered, and it may be difficult to achieve the target color concentration as a thin film.

(D) the polyfunctional monomer 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 trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, 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 preferable, and trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexa Acrylates are particularly preferred because they are excellent in pixel strength and surface smoothness, and are less likely to cause background contamination and 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 usage-amount of the polyfunctional monomer in this invention becomes like this. Preferably it is 5-500 weight part with respect to 100 weight part of (C) alkali-soluble resin, More preferably, it is 20-300 weight part. In this case, when the amount of the polyfunctional monomer used is less than 5 parts by weight, the strength and surface smoothness of the pixel tend to be reduced. On the other hand, when the amount exceeds 500 parts by weight, for example, alkali developability is reduced. In addition, background stains, film residue, etc. tend to occur on the unexposed portion of the substrate and the light shielding layer.
Moreover, in this invention, the monofunctional monomer which has one polymerizable unsaturated bond can also be used together with a polyfunctional monomer.
Examples of the monofunctional monomer include monomers similar to the carboxyl group-containing unsaturated monomer and copolymerizable unsaturated monomer exemplified for (C) the alkali-soluble resin, and N- (meta ) In addition to acryloyl morpholine, N-vinyl pyrrolidone, N-vinyl-ε-caprolactam, trade names include M-5600 (manufactured by Toagosei Co., Ltd.) and the like.
These monofunctional monomers can be used alone or in admixture of two or more.

The proportion of the monofunctional monomer used in the present invention is preferably 90% by weight or less, more preferably 50% by weight or less, based on the total amount of the polyfunctional monomer and the monofunctional monomer. is there. In this case, if the proportion of the monofunctional monomer used exceeds 90% by weight, the strength and surface smoothness of the pixel may be insufficient.
The total use amount of the polyfunctional monomer and the monofunctional monomer in the present invention is preferably 5 to 500 parts by weight, more preferably 20 to 300 parts per 100 parts by weight of the (C) alkali-soluble resin. Parts by weight. In this case, if the total amount used is less than 5 parts by weight, the strength and surface smoothness of the pixel tend to be lowered. On the other hand, if it exceeds 500 parts by weight, for example, alkali developability is lowered or There is a tendency that soiling, film residue, and the like are likely to occur on the substrate and the light shielding layer.

(E) Radiation-sensitive radical generator The photopolymerization initiator in the present invention is the above-mentioned (D) polyfunctional monomer and the case when exposed to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. Is a compound capable of generating an active species capable of initiating polymerization of a monofunctional monomer used.
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 etc. are preferable.
The acetophenone compounds can be used alone or in admixture of two or more.

  In the present invention, when the acetophenone compound is used as the photopolymerization initiator, the amount used is preferably 0 with respect to 100 parts by weight of the total of (D) the polyfunctional monomer and the monofunctional monomer. 0.01 to 100 parts by weight, more preferably 1 to 80 parts by weight, still more preferably 5 to 60 parts by weight. In this case, if the amount of the acetophenone compound used is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a colored layer in which the pixel pattern is arranged according to a predetermined arrangement, If it exceeds 100 parts by weight, the formed pixels tend to fall off the substrate during development.

  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, 2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like can be mentioned. .

  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 among these, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1 2,2′-biimidazole is particularly preferred.

The biimidazole compound is excellent in solubility in a solvent, does not generate foreign matters such as undissolved matter and precipitates, has high sensitivity, and sufficiently proceeds with a curing reaction by exposure with a small amount of energy, and is not exposed. Therefore, the exposed coating is clearly divided into a hardened portion that is insoluble in the developer and an uncured portion that has a high solubility in the developer. A high-definition colored layer in which pixel patterns without undercuts are arranged according to a predetermined arrangement can be formed.
The biimidazole compounds can be used alone or in admixture of two or more.

  In the present invention, the amount used when using a biimidazole compound as a photopolymerization initiator is preferably (D) with respect to a total of 100 parts by weight of the polyfunctional monomer and the monofunctional monomer. It is 0.01-40 weight part, More preferably, it is 1-30 weight part, More preferably, it is 1-20 weight part. In this case, if the amount of biimidazole compound used is less than 0.01 parts by weight, curing by exposure may be insufficient, and it may be difficult to obtain a colored layer in which a pixel pattern is arranged according to a predetermined arrangement, On the other hand, if it exceeds 40 parts by weight, the formed pixels tend to fall off the substrate during development.

-Hydrogen donor-
In the present invention, when a biimidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor described below 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.
As the hydrogen donor in the present invention, mercaptan compounds, amine compounds and the like defined below are preferable.
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- 2,5-dimethylaminopyridine and the like can be mentioned.
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. 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 are further preferable combinations. Are 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and the particularly preferred combination is 2-mercaptobenzothi Is a tetrazole / 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.

  In the present invention, when the hydrogen donor is used in combination with the biimidazole compound, the amount used is preferably 0 with respect to 100 parts by weight of the total of (D) the polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight. In this case, if the amount of the hydrogen donor used is less than 0.01 parts by weight, the effect of improving the sensitivity tends to decrease. On the other hand, if it exceeds 40 parts by weight, the formed pixels are likely to fall off the substrate during development. Tend.

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

  In the present invention, when the triazine compound is used as the photopolymerization initiator, the amount used is preferably 0 with respect to 100 parts by weight of the total of the (D) polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, still more preferably 1 to 20 parts by weight. In this case, if the amount of the triazine compound used is less than 0.01 parts by weight, curing by exposure may be insufficient, and it may be difficult to obtain a colored layer in which a pixel pattern is arranged according to a predetermined arrangement, If it exceeds 40 parts by weight, the formed pixels tend to drop off from the substrate during development.

-Additive component-
The radiation sensitive composition for a color filter in the present invention may contain various additive components as necessary.
The additive component may be an organic acid or an organic amino compound (provided to improve the solubility of the radiation-sensitive composition in an alkaline developer and to further suppress the remaining undissolved product after development) , Excluding the hydrogen donor).
The organic acid is preferably an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having one or more carboxyl groups in the molecule.

Examples of the aliphatic carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, and caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Examples thereof include aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid.

Examples of the phenyl group-containing carboxylic acid include compounds in which a carboxyl group is directly bonded to a phenyl group, and compounds in which a carboxyl group is bonded to a phenyl group via a divalent carbon chain.
Examples of the phenyl group-containing carboxylic acid include aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, and mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid,
Examples thereof include phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidene acid, coumaric acid, and umberic acid.

Among these organic acids, aliphatic carboxylic acids are aliphatic from the viewpoints of alkali solubility, solubility in a solvent described later, and prevention of soiling and film residue on the substrate and the light shielding layer in the unexposed area. Dicarboxylic acids are preferred, and malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are particularly preferred. As the phenyl group-containing carboxylic acid, an aromatic dicarboxylic acid is preferable, and phthalic acid is particularly preferable.
The organic acids can be used alone or in admixture of two or more.

  The amount of the organic acid used is preferably 15 parts by weight or less, more preferably 10 parts by weight or less with respect to 100 parts by weight of the total of the components (A) to (E) and the additive component. In this case, when the amount of the organic acid used exceeds 15 parts by weight, the adhesion of the formed pixel to the substrate tends to be reduced.

The organic amino compound is preferably an aliphatic amine or a phenyl group-containing amine having one or more amino groups in the molecule.
Examples of the aliphatic amine include mono (cyclo) such as n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, and n-hexylamine. Alkylamines;
Methyl ethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-sec- Di (cyclo) alkylamines such as butylamine, di-t-butylamine;
Dimethyl ethylamine, methyl diethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyl di-n-propylamine, ethyl di-n-propylamine, tri-n-propylamine, tri -Tri (cyclo) alkylamines such as i-propylamine, tri-n-butylamine, tri-i-butylamine, tri-sec-butylamine, tri-t-butylamine;
Mono (cyclo) alkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol;
Di (cyclo) alkanolamines such as diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine;
Tri (cyclo) alkanolamines such as triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine;
3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 Amino (cyclo) alkanediols such as 2, 2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol;
Examples thereof include aminocarboxylic acids such as β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, and 3-aminoisobutyric acid.

Examples of the phenyl group-containing amine include compounds in which an amino group is directly bonded to a phenyl group, and compounds in which an amino group is bonded to a phenyl group via a divalent carbon chain.
Examples of the phenyl group-containing amine include aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N- Aromatic amines such as diethylaniline, p-methyl-N, N-dimethylaniline;
aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;
Examples thereof include aminobenzoic acid such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid, and the like.

Among these organic amino compounds, mono (cyclo) alkanolamine is used as the aliphatic amine from the viewpoints of solubility in a solvent described later, prevention of soiling and film residue on the unexposed substrate and the light shielding layer, and the like. And amino (cyclo) alkanediol are preferred, among which 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1 3-propanediol, 4-amino-1,2-butanediol and the like are particularly preferable. As the phenyl group-containing amine, aminophenol is preferable, and o-aminophenol, m-aminophenol, p-aminophenol and the like are particularly preferable.
The organic amino compounds can be used alone or in admixture of two or more.
The amount of the organic amino compound used is preferably 15 parts by weight or less, more preferably 10 parts by weight or less with respect to 100 parts by weight of the total of the components (A) to (E) and the additive component. In this case, when the usage-amount of an organic amino compound exceeds 15 weight part, there exists a tendency for the adhesiveness to the board | substrate of the formed pixel to fall.

Examples of additive components other than those described above include 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-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone;
Anti-agglomerating agents such as sodium polyacrylate;
Examples thereof include a thermal radical generator such as 1,1′-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

(F) Solvent As the solvent in the present invention, the components (A) to (E) and additive components constituting the radiation-sensitive composition are dispersed or dissolved, and do not react with these components, and have an appropriate volatility. As long as it has, it can be appropriately selected and used.
Examples of such a solvent include alcohols such as methanol, ethanol, and 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 Can other esters;
Aromatic hydrocarbons such as toluene and xylene;
Examples 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-methyl Xylbutyl 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 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 high boiling point solvents can be used alone or in admixture of two or more.
The amount of solvent used is not particularly limited, but the total concentration of each component excluding the solvent of the composition is preferable from the viewpoints of applicability and storage stability of the resulting radiation-sensitive composition. Is preferably 5 to 50% by weight, more preferably 10 to 40% by weight.

-Preparation of radiation sensitive composition for color filter-
The method for preparing the radiation sensitive composition for a color filter of the present invention is not particularly limited, but (A) a pigment, (B) a dispersant, (C) an alkali-soluble resin, and (F) a solvent in advance. It is preferable to be dispersed 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”.
In the preliminary dispersion step, the amount of (C) alkali-soluble resin used is preferably 5 to 100% by weight, more preferably 10 with respect to the amount of (C) alkali-soluble resin used in the radiation sensitive composition for color filters. ~ 50% by weight. In this case, when the amount of the (C) alkali-soluble resin used is less than 5% by weight, the storage stability of the resulting composition tends to be reduced, or a residue tends to be generated on the substrate.
The pre-dispersing step can be performed, for example, by mixing the components using a mixing apparatus such as a dissolver, a bead mill, or a rod mill.
Following the pre-dispersing step, the pre-dispersed liquid is mixed with (D) a polyfunctional monomer and (E) a photopolymerization initiator, and optionally (C) an alkali-soluble resin and (F) the remainder of the solvent. The radiation sensitive composition for a color filter of the present invention can be obtained by mixing in the above.

Method for Forming Color Filter Next, a method for forming the color filter of the present invention using the radiation sensitive composition for color filters of the present invention (hereinafter also simply referred to as “radiation sensitive composition”) will be described. .
The method for forming a color filter of the present invention includes at least the following steps (1) to (4).
(1) The process of forming the film of the radiation sensitive composition of this invention on a board | substrate.
(2) A step of exposing radiation to at least a part of the coating.
(3) A step of developing the coated film after exposure.
(4) A step of post-baking the coating after development.
Hereinafter, these steps will be sequentially described.

-(1) Process-
First, on the surface of the substrate, if necessary, a light shielding layer is formed so as to divide the pixel forming portion, and after applying the radiation-sensitive composition of the present invention on this substrate, pre-baking is performed. The solvent is evaporated to form a film.
Examples of the substrate used in this step include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyethersulfone, cyclic olefin ring-opening polymer, and hydrogenated products thereof. it can.
In addition, these substrates may be subjected to known pretreatments 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.
When the radiation-sensitive composition is applied to the substrate, a known coating method such as spin coating, cast coating, roll coating or the like can be employed. A coating method using a spin coater or a slit die coater is preferred.
The prebaking conditions are preferably about 70 to 110 ° C. for about 2 to 4 minutes.
The coating thickness is preferably 0.1 to 8.0 [mu] m, more preferably 0.2 to 6.0 [mu] m, still more preferably 0.2 to 4.0 [mu] m, as the film thickness after drying.

-(2) Process-
Next, radiation is exposed to at least a part of the formed film. When exposing a part of the film in this step, it is preferably exposed through a photomask having a predetermined pattern.
As radiation used for exposure, for example, radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray can be appropriately selected and used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.
Exposure of radiation is preferably 10~10,000J / m ² approximately.

-(3) Process-
Next, the exposed film is developed using a developer, preferably an alkali developer, and the unexposed portion of the film is dissolved and removed to form a predetermined pattern.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5- An aqueous solution of diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is preferable to wash with water after alkali development.
As the development processing method, for example, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
The development conditions are preferably about 5 to 300 seconds at room temperature.

-(4) Process-
Subsequently, the substrate on which the pixel pattern is arranged in a predetermined arrangement can be obtained by post-baking the developed film.
As post-baking treatment conditions, for example, a temperature of 180 to 240 ° C. for about 15 to 90 minutes is preferable.
The film thickness of the pixel thus formed is preferably 0.1 to 6.0 μm, more preferably 0.5 to 3.0 μm.
By repeating the steps (1) to (4) using each radiation sensitive composition in which red, green or blue pigments are dispersed, red, green and blue pixel patterns are formed on the same substrate. Accordingly, a colored layer in which pixel patterns of the three primary colors of red, green, and blue are arranged in a predetermined arrangement can be formed on the substrate.
In the present invention, the order of forming the pixel patterns of the respective colors can be arbitrarily selected.

Color filter The color filter of the present invention is formed from the radiation-sensitive composition for a 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.

Color liquid crystal display device The color liquid crystal display device of the present invention comprises the color filter of the present invention.
The color 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. Furthermore, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed 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.

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

Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 2.7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid, N— After charging 25 parts by weight of phenylmaleimide, 45 parts by weight of benzyl methacrylate, 15 parts by weight of styrene, and 5 parts by weight of α-methylstyrene dimer (chain transfer agent), the reaction solution was heated to 80 ° C. while gently stirring. The temperature was raised to 3, and the polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and polymerization was continued for another 1 hour, whereby a resin solution ( Solid content concentration = 33.1 wt%) was obtained. The obtained resin was Mw = 15,000 and Mn = 7,000. This resin is referred to as “resin (B-1)”.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 1.5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol monomethyl ether acetate, followed by 20 parts by weight of methacrylic acid, N— Charge 25 parts by weight of phenylmaleimide, 30 parts by weight of benzyl methacrylate, 10 parts by weight of glycerol monomethacrylate, 15 parts by weight of styrene, and 2.5 parts by weight of α-methylstyrene dimer (chain transfer agent). While stirring, the temperature of the reaction solution was raised to 80 ° C., and this temperature was maintained for polymerization for 3 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.3 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the polymerization was continued for another hour, whereby a resin solution ( Solid content concentration = 33.0 wt%) was obtained. The obtained resin was Mw = 20,000 and Mn = 9,000. This resin is referred to as “resin (B-2)”.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 2.7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol monomethyl ether acetate, followed by 25 parts by weight of methacrylic acid and benzyl methacrylate. 75 parts by weight and 5 parts by weight of α-methylstyrene dimer (chain transfer agent) were charged, and after purging with nitrogen, the reaction solution was heated to 80 ° C. while gently stirring, and this temperature was maintained for 3 hours. Polymerized. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.3 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the polymerization was continued for another hour, whereby a resin solution ( Solid content concentration = 33.2% by weight) was obtained. The obtained resin was Mw = 17,000 and Mn = 8,600. This resin is referred to as “resin (B-3)”.

Example 1
(A) C.I. I. Pigment Red 242 and C.I. I. 30 parts by weight of a 70/30 (weight ratio) mixture with Pigment Red 254, (B) 10 parts by weight of Ajisper PB821 (solid content concentration 100.0% by weight) as a dispersant, (C) Resin (B- 1) A mixed solution consisting of 10 parts by weight and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent was mixed for 5 hours with a diamond fine mill (trade name, bead mill manufactured by Mitsubishi Materials Corporation, bead diameter 1.0 mm). Dispersed to prepare a pigment dispersion.
With respect to the obtained pigment dispersion, the average particle diameter of the pigment was measured by a dynamic light scattering method and found to be 140 nm.
Next, 400 parts by weight of this pigment dispersion, (C) 200 parts by weight of resin (B-2) as an alkali-soluble resin, (D) 60 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (E) radical A liquid composition comprising 40 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a generator and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent. (R1) was prepared.

Evaluation of rheological properties In a viscoelasticity measuring device ARES100FRT (manufactured by TA Instruments Inc.), the viscosity of the obtained liquid composition (R1) at a rotational speed of 0.5 to 500 (1 / s) is 23. Continuous measurement (rheological measurement) at ° C. From the result,
The rheological parameter (= {viscosity at shear 1.0 (1 / s)} / {viscosity at shear 100 (1 / s)}) was calculated.
When the rheology parameter is large, the difference in film thickness tends to increase between the central portion and the outer portion of the substrate, that is, the portion having a small share and the portion having a large share, and as a result, the coating property tends to be poor.
The rheological parameter was evaluated to be 1.25. A rheology parameter is said to be good if it is in the range of 1.0 to 1.5.

Evaluation of Storage Stability The viscosity of the obtained liquid composition (R1) was measured using an ELD viscometer manufactured by Tokyo Keiki Co., Ltd. Thereafter, the viscosities of the composition left at 40 ° C. for 1 week and that left at 23 ° C. for 1 month were measured. As a result, the viscosity immediately after preparation was 7.5 mPa · s, 8.0 mPa · s after 1 week at 40 ° C., and 7.8 mPa · s after 1 month at 23 ° C. If the viscosity is 20% or less based on the viscosity immediately after preparation, it can be said that the storage stability is good.
Next, two liquid compositions (R1) were applied on a 15 cm × 15 cm square soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface using a spin coater, and then heated at 90 ° C. Pre-baking was performed for 10 minutes in a clean oven to form a coating film having a thickness of 1.8 μm.

Next, after this substrate was cooled to room temperature, one of the two coated substrates was irradiated with 5 rays of radiation containing wavelengths of 365 nm, 405 nm, and 436 nm through a photomask using a high-pressure mercury lamp. The exposure was performed at an exposure amount of 1,000 J / m ² . Thereafter, the substrate is immersed in a developer comprising a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-baked at 230 ° C. for 30 minutes. The red stripe pixel pattern was formed on the substrate. The film thickness of this pixel was 1.50 μm. This substrate is used as a substrate for evaluating foreign matter, chromaticity, and ΔEab ^* characteristics.
Further, another coating film substrate was exposed to radiation containing each wavelength of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² without using a photomask using a high-pressure mercury lamp. . Thereafter, post-baking was performed at 230 ° C. for 30 minutes to form a solid red film on the substrate. The film thickness of this pixel was 1.50 μm. This substrate is used as a contrast ratio evaluation substrate.

Evaluation of foreign matter and chromaticity When the formed pixel pattern was observed with an optical microscope, no foreign matter was found on the pixel.
Further, when the chromaticity of the pixel was evaluated with a color analyzer MCPD2000 (manufactured by Otsuka Electronics Co., Ltd.), it was (x, y, Y) = (0.598, 0.354, 31.2).
Evaluation of contrast ratio The obtained substrate is sandwiched between two deflecting plates, and the front deflecting plate is rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, and the transmitted light intensity is measured by a luminance meter LS The maximum value and the minimum value were measured at −100 (manufactured by MINOLTA), and the contrast ratio was evaluated as 700 obtained by dividing the maximum value by the minimum value. It can be said that the contrast value is good if it exceeds 600.
ΔEab ^* Evaluation of characteristics In a substrate on which a red stripe pixel pattern is formed, the chromaticity of the central portion of the substrate and a portion of 5.5 cm diagonally from the central portion is measured with a color analyzer, and two locations are measured. The chromaticity difference ΔEab ^* was calculated.
The ΔEab ^* was evaluated to be 1.75. It can be said that ΔEab ^* is good if it is 3 or less.

Example 2
In Example 1, (A) C.I. I. Pigment Red 242 and C.I. I. A liquid composition (R2) was prepared in the same manner as in Example 1 except that 30 parts by weight of a 50/50 (weight ratio) mixture with Pigment Red 254 was used.
With respect to the obtained pigment dispersion, the average particle diameter of the pigment was measured by a dynamic light scattering method and found to be 130 nm. The rheological parameter was 1.21, and the viscosity immediately after preparation was 6.5 mPa · s, 6.9 mPa · s after 1 week at 40 ° C., and 6.7 mPa · s after 1 month at 23 ° C.
Further, in the same manner as in Example 1 except that the liquid composition (R2) was used, evaluation was performed by forming a red stripe pixel pattern having a thickness of 1.50 μm on the substrate.
As a result, no foreign matter was found on the pixels. The chromaticity of the pixel was (x, y, Y) = (0.598, 0.346, 29.2), the contrast ratio was 850, and ΔEab ^* was 2.10.

Comparative Example 1
In Example 1, 10 parts by weight of Solsperse S28000 (solid content concentration 100.0% by weight) was used instead of (B) dispersant PB821, and (C) resin instead of resin (B-1) as an alkali-soluble resin A liquid composition (r1) was prepared in the same manner as in Example 1 except that (B-3) was used.
With respect to the obtained pigment dispersion, the average particle diameter of the pigment was measured by a dynamic light scattering method and found to be 250 nm. The rheological parameter was 6.23. The viscosity immediately after preparation was 13.0 mPa · s, 25.0 mPa · s after 1 week at 40 ° C., and 20.0 mPa · s after 1 month at 23 ° C.
Further, in the same manner as in Example 1 except that the liquid composition (r1) was used, evaluation was performed by forming a red stripe pixel pattern having a thickness of 1.50 μm on the substrate.
As a result, no foreign matter was found on the pixels. The chromaticity of the pixel was (x, y, Y) = (0.598, 0.353, 30.0), the contrast ratio was 350, and ΔEab ^* was 8.05.

Comparative Example 2
In Example 1, a liquid composition (r2) was prepared in the same manner as in Example 1, except that the resin (B-3) was used instead of the resin (B-1) as the (C) alkali-soluble resin. .
With respect to the obtained pigment dispersion, the average particle diameter of the pigment was measured by a dynamic light scattering method and found to be 180 nm. The rheological parameter was 2.01, and the viscosity immediately after preparation was 9.5 mPa · s, 14.0 mPa · s after 1 week, and 12.5 mPa · s after 1 month at 23 ° C.
Further, in the same manner as in Example 1 except that the liquid composition (r2) was used, evaluation was performed by forming a red stripe pixel pattern having a thickness of 1.50 μm on the substrate.
As a result, no foreign matter was found on the pixels. The chromaticity of the pixel was (x, y, Y) = (0.598, 0.354, 30.5), the contrast ratio was 500, and ΔEab ^* was 3.01.

Claims (4)

  (A) a pigment, (B) a dispersant, (C) (c1) a carboxyl group-containing unsaturated monomer containing (meth) acrylic acid, (c2) an N-substituted maleimide, (c3) Styrene, α-methylstyrene, p-hydroxy-α-methylstyrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, A copolymer with at least one other copolymerizable unsaturated monomer selected from the group consisting of a polystyrene macromonomer and a polymethyl methacrylate macromonomer, (D) a polyfunctional monomer, (E) radiation sensitive A radiation-sensitive composition containing a reactive radical generator and (F) a solvent, wherein (A) the pigment is C.I. I. A radiation-sensitive composition for color filters, comprising 20% by weight or more of Pigment Red 242, and (A) the average particle diameter r (unit: nm) of the pigment is 50 ≦ r ≦ 200.   C. I. Pigment Red 242 containing 20% by weight or more and a pigment having an average particle size exceeding 200 nm are dispersed in a medium containing (B) a dispersant, (C) a copolymer, and (F) a solvent. The dispersion is mixed with (D) a polyfunctional monomer, (E) a radiation-sensitive radical generator, and (C) a copolymer and (F) a solvent as necessary. Preparation method of radiation sensitive composition.   A color filter formed from the radiation-sensitive composition for a color filter according to claim 1.   A liquid crystal display device comprising the color filter according to claim 3.