KR100907594B1 - Radiation-sensitive Composition for Color Filter, Method for Forming Colored Layer, Color Filter and Color Liquid Crystal Display Device - Google Patents

Abstract

The present invention provides a radiation-sensitive composition for color filters, a method for forming a colored layer formed therefrom, and a colored layer, which have a high transmittance and contrast ratio, and are capable of forming a red pixel having a high production yield on the formed pattern without generating foreign substances. It relates to a color filter to be provided, and also to a liquid crystal display device.

Description

Radiation-sensitive composition for color filter, method for forming colored layer, color filter and color liquid crystal display device}

The present invention relates to a radiation-sensitive composition for a color filter, a color filter and a color liquid crystal display device, and more particularly, a color filter perception useful for the production of a color filter used in a transmissive or reflective color liquid crystal display device, a color image tube device, or the like. A color filter and a color liquid crystal display device provided with the radiation composition and the colored layer formed from the radiation sensitive composition for color filters.

When manufacturing a color filter using a coloring radiation sensitive composition, the coating film of a coloring radiation sensitive composition is normally formed on the board | substrate or the board | substrate in which the light shielding layer of the desired pattern was previously formed, and then the mask which has a desired pattern shape Forming method of obtaining various pixels by irradiating radiation (hereinafter referred to as "exposure"), developing with an alkaline developer, dissolving and removing unexposed portions, and then baking using a clean oven or hot plate (Japanese Patent Japanese Patent Laid-Open No. 2-144502 and Japanese Patent Laid-Open No. 3-53201 are known.

The liquid crystal display device having such a color filter is required to have high luminance, and thus, a color filter has also recently been required to have a higher light transmittance. In addition, pixels and colored layers forming such color filters are increasingly required to have higher contrast. For this demand, it is known that C.I. Pigment Red 254 is particularly effective as a pigment used for red pixels, as disclosed in Japanese Patent Laid-Open No. 10-260309. However, when using the radiation sensitive composition containing C.I. Pigment Red 254, there existed a problem that a foreign material may arise on a red pattern, and a yield may fall sometimes.

Background Art A radiation sensitive composition for forming a red pixel which satisfies the recent high light transmittance and high contrast and does not generate foreign matter on a pattern and has a high production yield has not been known.

An object of the present invention is a color filter having a radiation-sensitive composition for a color filter that can produce a red pixel having a high transmittance and contrast ratio, does not generate foreign matter on the formed pattern and has a high manufacturing yield, and a color filter having a colored layer formed therefrom; It is an object of the present invention to provide a liquid crystal display device comprising the formation method and the color filter.

According to the present invention, the above object is first,

(A) a pigment, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photoradical generator, The said pigment (A) has an average particle diameter r (nm) of 100 <= r <= 300, It is also achieved by a radiation sensitive composition for color filters comprising CI pigment red 254.

Secondly, the above task

(1) Process of forming the coating film of the radiation sensitive composition for color filters in any one of Claims 1-3 on a board | substrate,

(2) irradiating at least a part of said coating film with radiation,

(3) developing process, and

(4) heating process

It is achieved by the method of forming a colored layer comprising a.

According to the present invention, the problem is third,

It is achieved by the color filter characterized by including the colored layer formed from the radiation sensitive composition for color filters.

According to the present invention, the fourth problem,

It is achieved by the color liquid crystal display device containing the colored layer formed from the radiation sensitive composition for color filters.

According to the present invention, a radiation-sensitive composition for color filters having a high transmittance and a contrast ratio and capable of forming a red pixel having a high production yield without generating foreign substances on the formed pattern, a method of forming a colored layer formed therefrom and the colored layer thereof There is provided a color filter comprising a liquid crystal display device.

The radiation sensitive composition for color filters of this invention can be used very favorably for manufacture of the apparatus which has various color filters, including the color liquid crystal display device of the electronic industry.

The present inventors have found that the above-mentioned problems of the prior art (generating foreign matter on a red pattern) frequently occur when high temperature treatment temperatures are employed in the colored layer forming process. In addition, even when the radiation-sensitive composition contains a pigment containing CI Pigment Red 254, if the pigment is in a specific particle size range, it has been found that even when treated at a high temperature, foreign matter does not occur and color characteristics are not impaired. The invention has been completed.

In addition, the term "radiation" in the present invention means that it includes visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

(A) pigment

The pigment used in the composition of the present invention has an average particle diameter r (nm) of 100 ≦ r ≦ 300, preferably 100 ≦ r ≦ 150, and further comprises C.I. Pigment Red 254.

If the average particle diameter of the pigment (A) exists in this range, even if CI pigment red 254 is contained in a pigment, the radiation sensitive composition containing such a pigment is a foreign material even if the process temperature in a colored layer formation process is 200 degreeC or more. It does not generate | occur | produce, and the process temperature of 230 degreeC or more, especially 250 degreeC or more can be employ | adopted.

Moreover, as distribution of the primary particle diameter of a pigment, it is preferable that the particle | grains which enter into average particle diameter +/- 100 nm are 70 weight% or more of the whole, and it is more preferable that this value is 80 weight% or more of the whole.

Generally, the higher the ratio of CI Pigment Red 254 contained in the pigment in the coloring composition, the more easily the problem of foreign matter generation occurs when the treatment temperature is set higher. Even if the ratio of the cement red 254 is 30 weight% or more, a foreign material does not generate | occur | produce, and the ratio can be 50 weight% or more, It is also possible to make it especially 60 weight% or more.

The pigment of the average particle diameter and particle size distribution as mentioned above is commercially available CI Pigment Red 254 (average particle diameter is more than 300 nm and 1000 nm or less) as needed Other pigment (average particle diameter is more than 300 nm and 1000 normally) nm or less), preferably by mixing and dispersing with a bead mill or a roll mill under suitable conditions in the presence of a dispersant or a solvent, to obtain a pigment dispersion.

As a dispersant used herein, a suitable dispersant of cationic, anionic, amphoteric, or nonionic type can be used, but preferably a dispersant containing a compound having a urethane bond (hereinafter referred to as "urethane-based dispersant") can be used. Can be.

Urethane bonds are generally of the formula R-NH-COO-R ', provided that R and R' are monovalent or polyvalent organic groups of aliphatic, cycloaliphatic or aromatic, and in the case of polyvalent organic groups have another urethane bond Groups or other groups, and may be present in the lipophilic and / or hydrophilic groups in the urethane-based dispersant, and may also be present in the main and / or side chains of the urethane-based dispersant, and also in one or more of the urethane-based dispersant. Can be. When two or more urethane bonds are present in a urethane-based dispersant, each urethane bond may be the same or different.

Examples of such urethane-based dispersants include reaction products of diisocyanates and / or triisocyanates with polyesters having hydroxy groups at one end and / or polyesters having hydroxy groups at both ends.

As said diisocyanate, For example, benzene diisocyanate, such as benzene-1, 3- diisocyanate and benzene-1, 4- diisocyanate; Toluene diisocyanates such as toluene-2,4-diisocyanate, toluene-2,5-diisocyanate, toluene-2,6-diisocyanate, toluene-3,5-diisocyanate; 1,2-xylene-3,5-diisocyanate, 1,2-xylene-3,6-diisocyanate, 1,2-xylene-4,6-diisocyanate, 1,3-xylene-2,4-di Isocyanate, 1,3-xylene-2,5-diisocyanate, 1,3-xylene-2,6-diisocyanate, 1,3-xylene-4,6-diisocyanate, 1,4-xylene-2,5 Aromatic diisocyanates, such as xylene diisocyanate, such as-diisocyanate and 1, 4- xylene-2, 6- diisocyanate, are mentioned, As said triisocyanate, For example, benzene-1,2,4 Benzene triisocyanates such as -triisocyanate, benzene-1,2,5-triisocyanate, benzene-1,3,5-triisocyanate; Toluene-2,3,5-triisocyanate, toluene-2,3,6-triisocyanate, toluene-2,4,5-triisocyanate, toluene-2,4,6-triisocyanate, toluene-3,4, Toluene triisocyanates such as 6-triisocyanate and toluene-3,5,6-triisocyanate, 1,2-xylene-3,4,6-triisocyanate, 1,2-xylene-3,5,6-triis Isocyanate, 1,3-xylene-2,4,5-triisocyanate, 1,3-xylene-2,4,6-triisocyanate, 1,3-xylene-3,4,5-triisocyanate, 1,4 And aromatic triisocyanates such as xylene triisocyanates such as -xylene-2,3,5-triisocyanate and 1,4-xylene-2,3,6-triisocyanate.

These diisocyanate and triisocyanate can be used individually or in mixture of 2 or more types, respectively.

Moreover, as polyesters which have a hydroxyl group in the said one end, or polyesters which have a hydroxyl group in both terminal, For example, polycaprolactone which has a hydroxyl group in one terminal or both terminal, Poly which has a hydroxyl group in one terminal or both terminal is mentioned, for example. Polylactones having a hydroxy group at one or both ends, such as valerolactone and polypropiolactone having a hydroxy group at one or both ends; And polycondensed polyesters having a hydroxy group at one or both ends, such as polyethylene terephthalate having a hydroxy group at one or both ends, and polybutylene terephthalate having a hydroxy group at one or both ends.

The polyester which has a hydroxyl group at these one terminal, and the polyester which has a hydroxyl group at both terminal can be used individually or in mixture of 2 or more types, respectively.

As the urethane-based dispersant of the present invention, a reaction product of aromatic diisocyanates with polylactones having a hydroxy group at one end and / or polylactones having a hydroxy group at both ends is preferable, and particularly toluene diisocyanates and one end Preference is given to reaction products with polycaprolactone having a hydroxy group at and / or polycaprolactone having a hydroxy group at both ends.

As a specific example of the urethane type dispersing agent which has at least one of the said characteristics, EFKA-46, East-47 (made by EFKA Chemicals Co., Ltd.), Disperbyk (BYK) by brand name, for example. Company), Disperon (Kumamoto Kasei Co., Ltd.), etc. are mentioned.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC) of the urethane-based dispersant of the present invention is usually 5,000 to 50,000, preferably 7,000 to 20,000.

In this invention, a urethane type dispersing agent can be used individually or in mixture of 2 or more types.

The amount of the urethane-based dispersant is usually 100 parts by weight or less, preferably 0.5 to 100 parts by weight, and more preferably 1 to 70 parts by weight based on 100 parts by weight of the total of CI Pigment Red 254 and other pigments added as necessary. And particularly preferably 10 to 50 parts by weight. In this case, when the usage-amount of a urethane type dispersing agent exceeds 100 weight part, performances, such as developability as a coloring resist, may be impaired.

In addition, as a solvent, the solvent similar to what is mentioned later can be used as a solvent which can be used for the radiation sensitive composition of this invention.

Such a solvent can be used in general from 500 to 1000 parts by weight, preferably 700 to 900 parts by weight, based on 100 parts by weight of the total of C.I. Pigment Red 254 and other pigments added as necessary.

In the case of performing the mixing and dispersing with a bead mill, glass beads, titania beads, and the like having a diameter of 0.5 to 10 mm are used, and a total of CI pigment red 254 and other pigments added as necessary, a dispersant, and a solvent are used. It can carry out by inject | pouring a mixed liquid into the bead mill.

The filling rate of the beads is usually 50 to 80%, and the injection amount of the mixed liquid is usually about 20 to 50% of the mill capacity. Dispersion time is about 2 to 4 hours normally.

Dispersion is preferably performed while cooling with cooling water or the like.

As a roll mill, a triaxial roll mill, a biaxial roll mill, etc. can be used. It is preferable that a roll space | interval is 10 micrometers or less, and a shear force is about 10 ⁸ dyn / sec normally.

Dispersion time is about 2 to 4 hours normally.

The average particle diameter of the pigment in the pigment dispersion liquid obtained as mentioned above and its distribution can be measured by the dynamic light scattering method.

In addition, the distribution of the average particle diameter of the pigment in a pigment dispersion liquid can be measured by the dynamic light scattering method.

As another pigment which (A) component of the radiation sensitive composition of this invention can contain, an organic pigment is preferable at the point which a color filter requires high purity, high permeability color development, and heat resistance.

As such other pigments, for example, compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colourists), specifically those having the following color index (CI) numbers are given. Can be.

CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI pigment yellow 166, CI pigment yellow 168, CI pigment yellow 211;

C.I. Pigment Orange 36, C.I.Pigment Orange 43, C.I.Pigment Orange 51, C.I.Pigment Orange 61, C.I.Pigment Orange 71;

CI Pigment Red 9, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Pigment Red 180, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 224, CI Pigment Red 242;

C.I. Pigment Violet 19, Pigment Violet 23, Pigment Violet 29;

C.I. Pigment Blue 15, C.I. Pigment Blue 60, C.I.Pigment Blue 15: 3, C.I.Pigment Blue 15: 4, C.I.Pigment Blue 15: 6,

C.I. pigment green 7, C.I. pigment green 36, C.I. pigment green 136, C.I. pigment green 210;

C.I. Pigment Brown 23, C.I.Pigment Brown 25.

These organic pigments can be used individually or in mixture of 2 or more types.

In addition, C.I. Pigment Red 254 and other organic pigments may be purified by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof.

(B) alkali soluble resin

As alkali-soluble resin (B) of this invention, it operates as a binder with respect to pigment (A), and also has solubility with respect to the developing solution used by the developing process at the time of manufacturing a color filter, Especially preferably an alkaline developing solution. Although it does not specifically limit if it is a thing, Alkali-soluble resin which has a carboxyl group is preferable, In particular, the ethylenically unsaturated monomer copolymerizable with another ethylenically unsaturated monomer which has 1 or more carboxyl groups (henceforth "carboxyl group-containing unsaturated monomer") (hereinafter, Preferred is a copolymer of "copolymerizable unsaturated monomer" (hereinafter referred to as "carboxyl group-containing copolymer").

As an example of a carboxyl group-containing unsaturated monomer,

Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid;

Unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid;

Trivalent or higher unsaturated polyvalent carboxylic acid or anhydrides thereof;

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 divalent or higher polyhydric carboxylic acid;

and mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -carboxy polycaprolactone monoacrylate and? -carboxy polycaprolactone monomethacrylate.

Among these carboxyl group-containing unsaturated monomers, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are the trademarks of M-5300 and M-5400 (manufactured by Toagosei Co., Ltd.), respectively. It is commercially available.

The said carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.

As the copolymerizable unsaturated monomer, for example,

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl Aromatic vinyl compounds such as ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and 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-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl Relate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxy Ethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol Methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, tricyclo [ 5.2.1.0 ^2,6] decane-8-yl acrylate, tricyclo [5.2.1.0 ^2,6] decane-8-yl methacrylate les Bit, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, unsaturated carboxylic acid esters, glycerol monoacrylate, glycerol monomethacrylate;

2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate Acid aminoalkyl esters;

Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate;

Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;

Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether;

Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;

Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide;

Unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide;

Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene;

Monoacryloyl group or monomethacryloyl group at the terminal of the polymer molecular chain, such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane The macromonomer which has, etc. are mentioned.

These copolymerizable unsaturated monomers can be used individually or in mixture of 2 or more types.

As the carboxyl group-containing copolymer of the present invention, (1) acrylic acid and / or methacrylic acid are essential components, and monosuccinic acid mono (2-acryloyloxyethyl) and monosuccinic acid mono (2-methacryloyl) are optionally used. Oxyethyl), a carboxyl group-containing unsaturated monomer component further containing at least one compound selected from the group of? -Carboxy polycaprolactone monoacrylate and? -Carboxy polycaprolactone monomethacrylate, (2) styrene, Methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monomethacrylate, 1 type selected from the group of glycerol monoacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethylmethacrylate macromonomer The copolymer with the above is preferable.

As a specific example of such a copolymer,

(Meth) acrylic acid / methyl (meth) acrylate copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate copolymers,

(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 / polymethylmethacrylate macromonomer copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate / polymethylmethacrylate 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 / polymethylmethacrylate macromonomer copolymer,

Methacrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer,

(Meth) acrylic acid / succinic mono [2- (meth) acryloyloxyethyl] / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer,

(Meth) acrylic acid / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer,

(Meth) acrylic acid / ω-carboxy polycaprolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer and the like.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, when the said copolymerization ratio is less than 5 weight%, the solubility with respect to the alkaline developing solution of the radiation sensitive composition obtained tends to fall, and when it exceeds 50 weight%, the solubility with respect to an alkaline developing solution will become excessive, When developing, the colored layer tends to fall off the substrate or cause film roughness of the pixel surface.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin is usually 3,000 to 300,000, preferably 5,000 to 100,000.

The polystyrene reduced number average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of alkali-soluble resin is usually 3,000 to 60,000, preferably 5,000 to 25,000. .

Moreover, ratio (Mw / Mn) of Mw and Mn of alkali-soluble resin becomes like this. Preferably it is 1-5, More preferably, it is 1-4.

In the present invention, a radiation-sensitive composition excellent in developability can be obtained by using an alkali-soluble resin having such specific Mw and Mn, whereby a pixel pattern having edges of sharp patterns can be formed. At the same time, residue, ground contamination, film residue, etc. do not occur on the substrate and the light shielding layer of the unexposed part during development.

In this invention, alkali-soluble resin (B) can be used individually or in mixture of 2 or more types.

The use amount of alkali-soluble resin (B) of this invention is 10-1,000 weight part normally with respect to 100 weight part of pigments (A), Preferably it is 20-500 weight part. In this case, when the usage-amount of alkali-soluble resin is less than 10 weight part, alkali developability may fall, for example, a background contamination and a film residue may arise on the board | substrate or the light shielding layer of an unexposed part, and 1,000 weight part When exceeding, since a pigment density falls relatively, it may become difficult to achieve the target color density as a thin film.

(C) Multifunctional  Monomer

The multifunctional monomer of the present invention is a monomer having two or more polymerizable unsaturated bonds.

As an example of a polyfunctional monomer,

Diacrylates or dimethacrylates of alkylene glycols such as ethylene glycol and propylene glycol;

Diacrylates or dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;

Polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and dicarboxylic acid modified substances thereof;

Oligo acrylates or oligo methacrylates such as polyesters, epoxy resins, urethane resins, alkyd resins, silicone resins and spiran resins;

Diacrylates or dimethacrylates of both terminal hydroxylated polymers such as both terminal hydroxy poly-1,3-butadiene, both terminal hydroxy polyisoprene and both terminal hydroxy polycaprolactone,

Tris (2-acryloyloxyethyl) phosphate, a tris (2-methacryloyl oxyethyl) phosphate, etc. are mentioned.

Of these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols or their dicarboxylic acid modified substances, specifically trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol Triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate Methacrylate and the like are preferred, and trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate are particularly excellent in the strength and surface smoothness of the colored layer, and on the substrate and the difference of the unexposed portion. Background contamination, the film on the layer is preferable because such a residue does not occur.

The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

The usage-amount of the polyfunctional monomer of this invention is 5-500 weight part normally with respect to 100 weight part of alkali-soluble resin (B), 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 colored layer tends to be lowered, while when it exceeds 500 parts by weight, for example, alkali developability is lowered or on the substrate of the unexposed part. Or background contamination, film residues, etc. tend to occur on the light shielding layer.

In addition, in this invention, one part of a polyfunctional monomer can also be substituted by the monofunctional monomer which has one polymerizable unsaturated bond.

As said monofunctional monomer, the same monomer as the carboxyl group-containing unsaturated monomer and copolymerizable unsaturated monomer which were illustrated with respect to alkali-soluble resin (B), N-acryloyl morpholine, N-methacryloyl morpholine, N, for example In addition to -vinylpyrrolidone and N-vinyl- epsilon caprolactam, M-5300, M-5400, M-5600 (brand name, Toagosei Co., Ltd.) etc. are mentioned as a commercial item.

These monofunctional monomers can be used individually or in mixture of 2 or more types.

The use ratio of a monofunctional monomer is 90 weight% or less normally with respect to the total amount of a polyfunctional monomer and a monofunctional monomer, Preferably it is 50 weight% or less. In this case, when the use ratio of a monofunctional monomer exceeds 90 weight%, there exists a possibility that the intensity and surface smoothness of the pixel obtained may become inadequate.

In addition, the total usage-amount of the polyfunctional monomer and monofunctional monomer of this invention is 5-500 weight part normally with respect to 100 weight part of alkali-soluble resin (B), Preferably it is 20-300 weight part. In this case, when the total amount used is less than 5 parts by weight, the strength and surface smoothness of the colored layer tends to decrease, while when the total amount exceeds 500 parts by weight, for example, alkali developability is lowered, or on the substrate or the light shielding layer of the unexposed part. Background contamination, film residue, etc. may occur easily.

(D) Photopolymerization Initiator

The photopolymerization initiator of the present invention is the (C) polyfunctional monomer and the monofunctional monomer used in some cases by irradiation (hereinafter referred to as "exposure") of visible light, ultraviolet ray, far ultraviolet ray, electron beam, X-ray, or the like. It is a compound which can generate | occur | produce the active species which initiates superposition | polymerization of.

As such a photoinitiator, an acetophenone type compound, a biimidazole type compound, a triazine type compound, a benzoin type compound, a benzophenone type compound, the (alpha)-diketone type compound, a polynuclear quinone type compound, a xanthone type compound, a diazo type compound, for example Etc. can be mentioned.

In the present invention, the photopolymerization initiator may be used alone or in combination of two or more thereof. As the photopolymerization initiator of the present invention, one or more selected from the group of acetophenone compounds, biimidazole compounds, and triazine compounds may be used. desirable.

The general usage-amount of the photoinitiator of this invention is 0.01-80 weight part normally with respect to a total of 100 weight part of (C) polyfunctional monomer and a monofunctional monomer, Preferably it is 1-60 weight part. In this case, when the usage-amount of a photoinitiator is less than 0.01 weight part, hardening by exposure may become inadequate, and it may become difficult to obtain the colored layer arrange | positioned according to a predetermined | prescribed arrangement, and when it exceeds 80 weight part, the pixel formed There is a tendency to fall off from the substrate during the development.

As a specific example of an acetophenone type compound among the preferable photoinitiators of this invention, 2-hydroxy-2- methyl-1- phenyl propane- 1-one, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy -1,2-diphenylethan-1-one etc. are mentioned.

Among these acetophenone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholine) Nophenyl) butanone-1 is preferred.

The acetophenone compounds may be used alone or in combination of two or more thereof.

In this invention, the usage-amount when using an acetophenone type compound as a photoinitiator is 0.01-80 weight part normally with respect to a total of 100 weight part of (C) polyfunctional monomer and a monofunctional monomer, Preferably it is 1-60. Parts by weight, more preferably 1 to 30 parts by weight. In this case, when the usage-amount of an acetophenone type compound is less than 0.01 weight part, hardening by exposure may become inadequate, and it may become difficult to obtain the pixel pattern in which the pixel arrange | positioned according to the predetermined arrangement, and when it exceeds 80 weight part, the coloring formed The layer tends to fall off the substrate during development.

Moreover, as a specific example of a biimidazole type compound,

2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,

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'-tetraphenyl-1,2'-biimidazole,

2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

2,2'-bis (2-bromophenyl) -4,4 ', 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 etc. are 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 More preferred are ', 5,5'-tetraphenyl-1,2'-biimidazole, especially 2,2'-bis (2,4-dichlorophenyl) -4,4'5,5'-tetraphenyl -1,2'-biimidazole is preferred.

The non-imidazole compound has excellent solubility in a solvent, does not generate foreign matters such as undissolved products, precipitates, etc., and also has a high sensitivity and sufficiently hardens the reaction by exposure of a small amount of energy. Since no curing reaction occurs, the coated film after exposure is clearly divided into a hardened portion insoluble in the developer and an uncured portion having high solubility in the developer, whereby pixels without undercuts are arranged according to a predetermined arrangement. A highly accurate pixel pattern can be formed.

The said biimidazole type compound can be used individually or in mixture of 2 or more types.

In this invention, the usage-amount when using a biimidazole type compound as a photoinitiator is 0.01-40 weight part normally with respect to a total of 100 weight part of (C) polyfunctional monomer and a monofunctional monomer, Preferably it is 1- 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, when the amount of the non-imidazole compound is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a pixel pattern in which pixels are arranged in a predetermined arrangement. There exists a tendency for the colored layer formed at the time of image development to fall off from a board | substrate.

Hydrogen donor

In this invention, when using a biimidazole type compound as a photoinitiator, using the following hydrogen donor together is preferable at the point which can improve a sensitivity further.

The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to radicals generated from a biimidazole compound by exposure.

As the hydrogen donor of the present invention, mercaptan compounds, amine compounds and the like defined below are preferable.

The mercaptan compound has a benzene ring or a heterocycle as a mother nucleus, and has at least one, preferably one to three, more preferably one to two mercapto groups directly bonded to the mother nucleus (hereinafter, “ Mercaptan-based hydrogen donors ".

In addition, the amine-based compound has a benzene ring or a heterocycle as a mother nucleus, and a compound having at least one, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter, &Quot; amine-based hydrogen donors ").

These hydrogen donors may also have a mercapto group and an amino group at the same time.

Hereinafter, these hydrogen donors will be described in more detail.

The mercaptan-based hydrogen donor may have one or more benzene rings or heterocycles, and may also have both benzene rings and heterocycles, and in the case of having two or more of these rings, it may or may not form a condensed ring. have.

In addition, when the mercaptan-based hydrogen donor has two or more mercapto groups, as long as one or more free mercapto groups remain, one or more of the remaining mercapto groups may be substituted with an alkyl, aralkyl or aryl group, and also one As long as the above free mercapto group remains, two sulfur atoms may have a structural unit bonded via a divalent organic group such as an alkylene group, or two sulfur atoms in a form of disulfide.

The mercaptan-based hydrogen donor may be substituted by 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 portion other than the mercapto group.

Specific examples of such mercaptan-based hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2 Mercapto-2,5-dimethylaminopyridine and the like.

Among these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzooxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

Subsequently, the amine-based hydrogen donor may have one or more benzene rings or heterocycles, and may have both benzene rings and heterocycles, and in the case of having two or more rings, it may form or may not form a condensed ring. It may not.

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 at a portion other than the amino group, a carboxyl group, alkoxycarbonyl group, substituted alkoxycarbonyl group, phenoxycarbonyl group, substituted phenoxycarbonyl group and nitrile group Or the like.

Specific examples of such amine hydrogen donors include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, and 4-dimethylaminopropiophenone. , Ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile, and the like.

Among these amine-based hydrogen donors, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone are preferable, and 4,4'-bis (diethylamino) benzophenone is particularly preferred. This is preferred.

The amine hydrogen donor has a function as a sensitizer even in the case of photoinitiators other than a biimidazole type compound.

In the present invention, the hydrogen donor may be used alone or in combination of two or more thereof, but a colored layer formed by using one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors in combination may be formed on the substrate during development. It is preferable at the point that it does not drop off and the intensity | strength and the sensitivity of a colored layer are also high.

Specific examples of the combination of the mercaptan-based hydrogen donor and the amine-based hydrogen donor include 2-mercaptobenzothiazole / 4,4'-bis (dimethylamino) benzophenone and 2-mercaptobenzothiazole / 4,4'-bis (Diethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) benzophenone Etc., and more preferable combinations include 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone and 2-mercaptobenzooxazole / 4,4'-bis (diethylamino ) Benzophenone, and 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone is mentioned as an especially preferable combination.

The weight ratio of the mercaptan-based hydrogen donor and the amine-based hydrogen donor in the combination of the mercaptan-based hydrogen donor and the amine-based hydrogen donor is usually 1: 1 to 1: 4, preferably 1: 1 to 1: 3.

In the present invention, the amount used when the hydrogen donor is used in combination with the biimidazole-based compound is preferably 0.01 to 40 parts by weight, more preferably based on 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer. Is 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. In this case, when the amount of the hydrogen donor used is less than 0.01 part by weight, the effect of improving the sensitivity tends to be lowered, while when it exceeds 40 parts by weight, the formed colored layer tends to fall off the substrate during development.

Moreover, as a specific example of the said triazine type compound,

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 (trichloromethyl) -s-triazine,

2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine,

2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine,

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine,

2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine,

And triazine-based compounds having halomethyl groups, such as 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.

Among these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine and the like are preferable.

The said triazine type compound can be used individually or in mixture of 2 or more types.

In the present invention, the amount used in the case of using a triazine-based compound as the photopolymerization initiator is preferably 0.01 to 40 parts by weight, more preferably 1 to 100 parts by weight in total of the (C) polyfunctional monomer and the monofunctional monomer. To 30 parts by weight, particularly preferably 1 to 20 parts by weight. In this case, when the amount of the triazine-based compound used is less than 0.01 part by weight, curing by exposure may be insufficient, and it may be difficult to obtain a pixel pattern in which pixels are arranged according to a predetermined arrangement. It tends to fall off from a substrate at this time.

Optional ingredients

The radiation sensitive composition for color filters of this invention may contain various arbitrary additional components as needed.

As said optional addition component, the organic acid or organic amino compound which shows the effect which further improves the dissolution characteristic with respect to the alkaline developing solution of a radiation sensitive composition, and further suppresses the remainder of the undissolved matter after image development (except the said hydrogen donor) And other optional ingredients.

Organic acids

As said organic acid, the aliphatic carboxylic acid or phenyl group containing carboxylic acid which has one or more carboxyl groups in molecular weight, and whose molecular weight is 1,000 or less is preferable.

As an example of the said aliphatic carboxylic acid,

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, brasilic 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 and mesaconic acid;

Aliphatic tricarboxylic acids, such as tricarvalic acid, aconitic acid, and camphoronic acid, etc. are mentioned.

Examples of the phenyl group-containing carboxylic acid include compounds in which a carboxyl group is directly bonded to a phenyl group, compounds in which the carboxyl group is bonded to a phenyl group through a carbon chain, and the like.

As an example of a phenyl group containing carboxylic acid,

Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid;

Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid;

Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, meropanic acid and pyromellitic acid;

And phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropaic acid, cinnamic acid, cinnamiledic acid, kumaric acid, and umbelic acid.

Among these organic acids, aliphatic dicarboxylic acids are preferable as aliphatic carboxylic acids from the viewpoint of alkali solubility, solubility in a solvent to be described later, background contamination on the substrate or the light shielding layer of the unexposed portion, and prevention of film residue. , Adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are preferable, and as the phenyl group-containing carboxylic acid, aromatic dicarboxylic acids are preferable, and phthalic acid is particularly preferable.

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

The usage-amount of an organic acid is 15 weight% or less normally with respect to the total amount of each component of (A)-(D) and arbitrary addition components, Preferably it is 10 weight% or less. In this case, when the usage-amount of an organic acid exceeds 15 weight%, there exists a tendency for adhesiveness with respect to the board | substrate of the formed colored layer to fall.

Organic Amino Compounds

Moreover, as said organic amino compound, the aliphatic amine or phenyl group containing amine which has 1 or more amino group in a molecule | numerator is preferable.

As an example of the said aliphatic amine,

mono (cyclo) alkylamines such as n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine and n-hexylamine;

Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di- di (cyclo) alkylamines such as sec-butylamine and di-t-butylamine;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, tri tri (cyclo) alkylamines such as -i-propylamine, tri-n-butylamine, tri-i-butylamine, tri-sec-butylamine and tri-t-butylamine;

Mono (cyclo) alkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, and 4-amino-1-butanol;

Di (cyclo) alkanolamines such as diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine and di-i-butanolamine;

Tri (cyclo) alkanolamines such as triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine and 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-1,2 Amino (cyclo) alkanediols such as propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, and 2-diethylamino-1,3-propanediol ;

and aminocarboxylic acids such as β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, and 3-aminoisobutyric acid.

Moreover, as a phenyl group containing amine, the compound etc. which the amino group couple | bonded with the phenyl group directly, the amino group couple | bonded with the phenyl group via the carbon chain, etc. are mentioned, for example.

As an example of a phenyl group containing amine,

Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p Aromatic amines such as -methyl-N, N-dimethylaniline;

aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol and p-diethylaminobenzyl alcohol;

aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol and p-diethylaminophenol;

and aminobenzoic acids (derivatives) such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid.

Among these organic amino compounds, mono (cyclo) alkanolamines and amino (cyclo) alkanediols are used as aliphatic amines from the viewpoints of solubility in a solvent to be described later, background contamination on the substrate or the light shielding layer of the unexposed portion, and prevention of film residue. Preference is given to, in particular, 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 etc. are preferable, and as a phenyl group containing amine, aminophenols are preferable, and o-aminophenol, m-aminophenol, p-aminophenol, etc. are especially preferable.

The said organic amino compound can be used individually or in mixture of 2 or more types.

The usage-amount of an organic amino compound is 15 weight% or less normally with respect to the total amount of each component of (A)-(D) and arbitrary addition components, Preferably it is 10 weight% or less. In this case, when the usage-amount of an organic amino compound exceeds 15 weight%, there exists a tendency for adhesiveness with the board | substrate of the formed colored layer to fall.

-Other optional ingredient-

In addition, as other optional components, for example

Dispersion aids such as blue pigment derivatives such as copper phthalocyanine derivatives and yellow pigment derivatives;

Fillers such as glass and alumina;

Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers, and poly (fluoroalkyl acrylates);

Surfactants such as nonionic, cationic and anionic systems;

Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimeth Adhesion promoters such as oxysilane;

Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol;

Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones;

Aggregation inhibitors such as sodium polyacrylate;

And thermal radical generators such as 1,1'-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

menstruum

The radiation sensitive composition for color filters of this invention makes said (A)-(D) component an essential component, and contains the said optional addition component as needed, but is normally manufactured as a liquid composition by mix | blending a solvent.

As said solvent, if (A)-(D) component and additive component which comprise a radiation sensitive composition are disperse | distributed or melt | dissolved, and it does not react with these components, and has moderate volatility, it can select suitably, and can use.

As a specific example of such a solvent,

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, propylene glycol mono-n-propyl ether, propylene glycol Mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene (Poly) alkylene glycol monoalkyl such as glycol monoethyl ether Ethers;

(Poly) alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate Glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate;

Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 Methyl hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, acetic acid n -Butyl, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-pyruvate Other esters such as propyl, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate;

Aromatic hydrocarbons such as toluene and xylene;

Amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and the like.

Propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, di Ethylene glycol methylethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3- Methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, butyric acid i-propyl, butyric acid n-butyl, pyruvic acid Ethyl and the like are preferred.

The said solvent can be used individually or in mixture of 2 or more types.

In addition, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, together with the solvent High boiling point solvents, such as diethyl oxalate, diethyl maleate, gamma -butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate, can also be used together.

These high boiling point solvents can be used individually or in mixture of 2 or more types.

Although the usage-amount of a solvent is not specifically limited, From the viewpoint of the coating property, stability, etc. of the radiation sensitive composition obtained, the total concentration of each component except the solvent of the said composition is 5-50 weight% normally, Preferably it is 10-40 weight. The amount which becomes% is preferable.

Colored layer  Formation method

Next, the method to form a colored layer using the radiation sensitive composition for color filters of this invention is demonstrated.

The step of forming the colored layer includes at least the following steps.

(1) Process of forming the coating film of the radiation sensitive composition for color filters of this invention on a board | substrate

(2) irradiating at least a part of the coating film with radiation

(3) developing process

(4) heating process

Hereinafter, it demonstrates sequentially.

(1) The coating film of the radiation sensitive composition for color filters of this invention Formation on the substrate .

A light shielding layer is formed on the substrate surface so as to partition a portion for forming a pixel, if necessary, and a liquid composition of, for example, a radiation-sensitive composition in which a red pigment is dispersed, is applied to the substrate, followed by prebaking. Can be evaporated and a coating film can be formed.

As a board | substrate which can be used here, the ring-opening polymer of glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyether sulfone, and cyclic olefin, and its hydrogenated substance etc. are mentioned, for example. have.

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

When apply | coating a radiation sensitive composition to a board | substrate, the appropriate application | coating methods, such as rotational coating, casting | flow_spread coating, roll coating, can be used.

As conditions for prebaking, it is about 2 to 4 minutes at 70-110 degreeC normally.

The coating thickness is usually 0.1 to 10 mu m, preferably 0.2 to 8.0 mu m, particularly preferably 0.2 to 6.0 mu m as the film thickness after solvent removal.

(2) above Of coating film  Irradiating at least a part of it

Then, a part of the coating film formed as mentioned above is exposed through the photomask which has a suitable pattern, for example. As the radiation used at this time, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

The exposure dose of radiation is preferably 10 to 10,000 J / m ² .

(3) developing process

Then, it develops using alkaline developing solution and removes and removes the unexposed part of a coating film. Examples of the alkaline developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabi, and the like. Aqueous solutions, such as cyclo- [4.3.0] -5-nonene, are preferable.

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkaline developer. In addition, after alkali development, water washing is normally performed.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid dipping) developing method, and the like can be applied. As for image development conditions, 5 to 300 second is preferable at normal temperature.

(4) heating process

Thereafter, by heating (postbaking), the pixel pattern in which the red pixels are arranged in a predetermined array can be formed. As conditions of a heating process, about 20 to 40 minutes are preferable at 180-230 degreeC.

By repeating the above steps (1) to (4) in the same manner using each radiation-sensitive composition in which green or blue pigments are dispersed, a coating film formation, exposure, development and heating step of each color tone material are performed, and a green pixel is obtained. By forming the pattern and the blue pixel pattern on the same substrate, it is possible to obtain a colored layer in which the three primary color pixel patterns of red, green and blue are arranged on the substrate.

In addition, the formation order of the pixel pattern of each color is not limited to the above-mentioned order.

Color filter

The color filter of this invention is equipped with the colored layer obtained in this way. Therefore, the color filter of the present invention has a high red transmittance and contrast ratio and includes a red pixel pattern on which no foreign matter is generated on the formed pattern.

The film thickness of the red pixel pattern which the color filter of this invention has is 0.5-5.0 micrometers, Preferably it is 1.5-3.0 micrometers.

The red pixel pattern of the color filter of the present invention can have a contrast ratio of 500 or more, preferably 600 or more when the film thickness is 1.50 占 퐉 and no foreign matter is generated on the formed pattern. In addition, although it is conventionally known that when the average particle diameter r of the pigment to be used may be less than 100 nm, it is known conventionally, but the red pixel which has a contrast ratio of 500 or more and does not generate | occur | produce a foreign material on the formed pattern and it is formed The radiation sensitive composition for color filters for that is not known conventionally.

Therefore, the color filter of this invention is very useful, for example in a transmissive or reflective color liquid crystal display device, a color imaging tube element, a color sensor, etc.

In addition, the contrast ratio measures a maximum value and a minimum value of light intensity transmitted by rotating the front side deflection plate while irradiating a fluorescent lamp from the back side by sandwiching a substrate having the formed pixel pattern between two deflection plates, and measuring the maximum value and the minimum value. It can be measured as a value divided by.

Color liquid crystal display

The color liquid crystal display device of this invention is equipped with the colored layer formed as mentioned above from the radiation sensitive composition for color filters of this invention.

The color liquid crystal display device of this invention can take a suitable structure.

For example, the color filter may be manufactured on a substrate separate from the driving substrate on which the thin film transistor TFT is disposed, and the driving substrate and the color filter substrate may be opposed to each other through the liquid crystal layer.

In addition, a substrate in which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped tin) electrode is formed may be opposed to each other through a liquid crystal layer. have. The latter structure can significantly improve the aperture ratio, and has the feature of providing a bright and accurate display element.

<Example>

Hereinafter, an Example is given and embodiment of this invention is described further more concretely. However, the present invention is not limited to the following examples.

<Example 1>

40 parts by weight of a 65/35 (weight ratio) mixture of CI Pigment Red 254 and CI Pigment Yellow 139 as pigment (A), (B) 10 parts by weight of EFKA-47 (manufactured by ZENEKA) as a dispersant, (C) as solvent 100 parts by weight of a pigment dispersion obtained by stirring a mixed liquid containing 100 parts by weight of ethyl 3-ethoxypropionate with a diamond fine mill (trade name, manufactured by Mitsubishi Material Co., Ltd.) for 2 hours, (D) methacrylic acid / Styrene / benzyl methacrylate / glycerol monomethacrylate / N-phenylmaleimide copolymer (copolymer weight ratio = 15/15/35/10/25, Mw = 30,000, Mn = 10,000) 70 parts by weight, (E) shell 80 parts by weight of dipentaerythritol hexaacrylate as the functional monomer, (F) 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as the photopolymerization initiator and propylene glycol as a solvent Radiation-sensitive by mixing 1,000 parts by weight of monomethyl ether acetate A hydrous product (R1) was prepared.

Moreover, it was 600 nm when the average particle diameter before dispersion of the pigment mixture used above was measured by the dynamic light scattering method. On the other hand, the average particle diameter of the pigment dispersion liquid after dispersion processing was 100 nm, and the particle | grains of particle size 200 nm or less were 81% of the whole.

<Formation of Red Pixel Patterns>

After applying a radiation sensitive composition (R1) using a spin coater on the surface of a soda glass substrate having a SiO ₂ film formed thereon to prevent elution of sodium ions on the surface, the film thickness was prebaked for 10 minutes in a clean oven at 90 ° C. A 2.0 micrometer coating film was formed.

Subsequently, after cooling the substrate to room temperature, a high-pressure mercury lamp was used to expose radiation, including each wavelength of 365 nm, 405 nm and 436 nm, to the coating film through a photomask at an exposure dose of 5,000 J / m ² . It was. Thereafter, the substrate was immersed in a developer containing a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air dried, and then baked at 250 ° C. for 30 minutes to form a red striped pixel on the substrate. A pattern was formed. The film thickness of this pixel pattern was 1.60 micrometers.

<Evaluation of Foreign Matter>

When the obtained pixel pattern was observed with the optical microscope, a foreign material was not confirmed on the pattern.

When the chromaticity of the pixel pattern was evaluated by color analyzer TC-1800M (manufactured by Tokyo Denshoku Co., Ltd.), it was (x, y, Y) = (0.650, 0.325, 19.1).

<Evaluation of contrast ratio>

The substrate having the pixel pattern formed as described above was sandwiched between two deflection plates and the maximum and minimum values of light intensity transmitted by rotating the front deflection plate while measuring fluorescent lamps from the rear side were measured. The value obtained by dividing the maximum value at this time by the minimum value was defined as "contrast ratio", which was 730.

<Example 2>

A radiation sensitive composition (R2) was produced in the same manner as in Example 1 except that the stirring time of the pigment dispersion in Example 1 was set to 1 hour.

When the average particle diameter of the pigment dispersion liquid after the dispersion treatment used here was measured by the dynamic light scattering method, the particles having a particle size of 50 to 250 nm were 68% of the whole.

Except having used the radiation sensitive composition (R2), it carried out similarly to Example 1, and formed and evaluated the red stripe-shaped pixel pattern of thickness 1.60 micrometers on the board | substrate, and, as a result, only a very small quantity of the foreign material on the pattern was confirmed. The number of foreign matters was an average of four in the range of 100 micrometer x 100 micrometers.

Moreover, when the chromaticity of the pixel pattern was evaluated, (x, y, Y) = (0.650, 0.325, 19.0). The contrast ratio was 650.

Comparative Example 1

A radiation sensitive composition (r1) was produced in the same manner as in Example 1 except that the stirring time of the pigment dispersion liquid was changed to 5 hours in Example 1. Except having used this radiation sensitive composition (r1), it carried out similarly to Example 1, and formed and evaluated the red stripe type pixel pattern with a thickness of 1.60 micrometers on the board | substrate.

When the chromaticity of the pixel pattern was evaluated, it was (x, y, Y) = (0.650, 0.326, 19.3). Although the contrast ratio was high as 1,100, the foreign material generate | occur | produced on the pattern. The number of foreign matters was an average of 80 in the range of 100 micrometers x 100 micrometers, and was unsuitable as a pixel used for a display element.

Moreover, when the average particle diameter of the pigment dispersion liquid after dispersion processing was measured by the dynamic light scattering method, it was 40 nm, and the particle | grains whose particle diameter was 140 nm or less were 82% of the whole.

<Example 3>

50 parts by weight of a 50/20/30 (weight ratio) mixture of CI Pigment Red 254, CI Pigment Red 177, and CI Pigment Yellow 139 as pigment (A) used for the dispersion treatment, (B) BYK-162 ( A liquid composition (R3) of the radiation sensitive composition was produced in the same manner as in Example 1, except that 10 parts by weight of Big Chemistry Co., Ltd. was used.

When the average particle diameter before dispersion of the pigment mixture used here was measured by the dynamic scattering method, it was 500 micrometers, and the particle | grains of the range of 400-600 micrometers were 51% of the whole. On the other hand, the average particle diameter of the pigment dispersion liquid after dispersion processing was 110 nm, and the particle | grains of particle size 210 nm or less were 79% of the whole.

Except having used the liquid composition (R2), it carried out similarly to Example 1, and formed and evaluated the red striped pixel pattern of thickness 1.60 micrometers on the board | substrate, and the foreign material was not recognized on the pattern. When the chromaticity of the pixel pattern was evaluated, (x, y, Y) = (0.650, 0.326, 19.1). In addition, the contrast ratio was 700.

Comparative Example 2

A radiation sensitive composition (r2) was produced in the same manner as in Example 3 except that the dispersion treatment of the pigment mixture was not performed in Example 3.

Except having used the radiation sensitive composition (r2), it carried out similarly to Example 1, and formed and evaluated the red striped pixel pattern of thickness 1.60 micrometers on the board | substrate, and the foreign material generation was not confirmed on the pattern. However, when the chromaticity of the pixel pattern was evaluated, (x, y, Y) = (0.650, 0.322, 17.5), the luminance Y value was low, and the contrast ratio was 350, and it was not possible to use it as a pixel used for a display element. .

According to the present invention, a radiation-sensitive composition for color filters having a high transmittance and a contrast ratio and capable of forming a red pixel having a high production yield without generating foreign substances on the formed pattern, a method of forming a colored layer formed therefrom and the colored layer thereof There is provided a color filter comprising a liquid crystal display device.

The radiation sensitive composition for color filters of this invention can be used very favorably for manufacture of the apparatus which has various color filters, including the color liquid crystal display device of the electronic industry.

Claims (7)

(A) a pigment, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) optical radical generator, and said pigment (A) has an average particle diameter r (nm) measured by the dynamic light scattering method 100 ≤ r ≤ 300, the average particle diameter ± 100 nm, the total amount of particles is 70% by weight or more, the radiation-sensitive composition for color filters containing CI Pigment Red 254, the pigment (A) is CI pigment A mixture of pigment red 254 or CI pigment red 254 with other pigments is obtained by reacting toluene diisocyanates with polycaprolactone having a hydroxy group at one end, polycaprolactone having a hydroxy group at both ends or a mixture thereof. Persimmon for color filters, which is produced in the form of a pigment dispersion by mixing and dispersing in the presence of a dispersant and a solvent containing 10 to 50 parts by weight with respect to 100 parts by weight. Diagonal composition. The radiation sensitive composition for color filters of Claim 1 whose content of C.I. pigment red 254 in pigment (A) is 30 weight% or more. The alkali-soluble resin (B) according to claim 1, wherein (1) acrylic acid and / or methacrylic acid are essential components, succinic mono (2-acryloyloxyethyl) and succinic acid mono (2-methacryl). Royloxyethyl), a carboxyl group-containing unsaturated monomer component which may further contain at least one compound selected from the group of? -Carboxy polycaprolactone monoacrylate and? -Carboxy polycaprolactone monomethacrylate, and (2 Styrene, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol mono At least one selected from the group of methacrylate, glycerol monoacrylate, N-phenylmaleimide, polystyrene macromonomers and polymethylmethacrylate macromonomers The radiation-sensitive polymer composition for a color filter. (1) Process of forming the coating film of the radiation sensitive composition for color filters in any one of Claims 1-3 on a board | substrate, (2) irradiating at least a part of said coating film with radiation, (3) developing process, and (4) heating process Forming method of the colored layer comprising a. The color filter formed from the radiation sensitive composition for color filters in any one of Claims 1-3. The color filter characterized by the above-mentioned. The color liquid crystal display device containing the colored layer formed from the radiation sensitive composition for color filters in any one of Claims 1-3. The color of Claim 1 whose average particle diameter r (nm) measured by the dynamic light-scattering method of the said pigment (A) is 100 <= r <= 150, and the particle | grains which fall in average particle diameter +/- 100 nm are 70 weight% or more of the whole. Radiation-sensitive composition for filters.