JPH0239155A - Colored pattern forming method - Google Patents

Abstract

PURPOSE:To obtain a colored pattern suitable for use as black stripes having low light transmissivity and superior resolution especially in case of black by using specified dyeable radiation-sensitive resin in the form of a thin film having superior dyeability. CONSTITUTION:A substrate is coated with dyeable radiation-sensitive resin contg. a copolymer of vinyllactams with a monomer having the structure of quat. amine and a polymerizable unsatd. bond and (meth)acrylic ester. The coated substrate is irradiated with radiation and a pattern is formed by development and dyed with an acidic azo dye contg. a metallic complex salt to obtain a colored pattern. Though the colored pattern is formed by dyeing the pattern made of the dyeable material, high dyeability is ensured even in case of about 1mum thickness. Black stripes having superior light shielding property can be formed especially by dyeing the pattern black.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for forming a colored pattern, and in particular to a colored pattern suitable for forming black stripes on color separation filters for various color image sensors and color liquid crystal displays. The present invention relates to a method of forming.

[Conventional technology]

In recent years, the display quality of color LCD displays has improved significantly and compact color TVs have been commercialized, but in order to achieve display quality comparable to that of conventional cathode ray tubes (CRTs), better color reproducibility and display contrast are needed. Excellent products are required.

As a means to further improve this display quality, there is a method to improve the display contrast by covering the part of the color separation filter other than each display pixel with a pattern of one color black to form a black stripe and preventing light leakage. Are known.

A known method for forming this blank drive is to form black stripes by overlapping different colors of color separation filters, such as red, blue, and green, so that they appear black, but alignment is difficult. Otherwise, the surface of the color separation filter may become extremely uneven, making it impossible to obtain a satisfactory display performance.

In addition, in consideration of mass production of color separation filters, attempts have been made to dye patterns made of dyeable material black to form flux stripes, but this method is not suitable for conventional dyeable pattern forming materials. Gelatin, casein, and the like have a problem in that black stripes with a thin film (about 1 μm) and low light transmittance cannot be produced.

(Problems to be Solved by the Invention) The present invention was made against the background of the above-mentioned conventional technical problems. An object of the present invention is to provide a method for forming a colored pattern suitable as an excellent black stripe.

[Means to solve the problem]

The present invention provides (a) vinyl lactams (hereinafter sometimes referred to as "component (a)"), (b) monomers having a quaternary amine structure and a polymerizable unsaturated bond (hereinafter referred to as "component (a)").
(hereinafter simply referred to as "copolymer") with (c) (meth)acrylic acid ester (hereinafter referred to as "component (c)") A method of forming a colored pattern is provided in which a dyeable radiation-sensitive resin containing a dye is applied to a substrate, irradiated with radiation, developed to form a pattern, and then dyed with an azo acid dye containing a metal complex salt. This is what we provide.

Examples of the fal component used in the copolymer of the present invention include compounds represented by the following structure (I) or (II).

HC=CH2 / (wherein, R1 and R7 may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or pentyl group. ) Specific examples of component (a) include N-vinyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, and
N-vinyl lactams such as -vinyl-2-piperidone can be mentioned.

Among these (al components), N-vinyl-2-pyrrolidone is particularly preferred.

In addition, as the (bl component, for example, the following - structure (III
) can be mentioned.

/ \ I2 ・ ・ ・ ・ ・ ・ (III) (in the formula, R8
is a hydrogen atom or a methyl group, R9 is a divalent organic group, R''
~R13 may be the same or different (, hydrogen atom or monovalent organic group, Z is an oxygen atom or imino group, X- represents an anion species capable of forming an ammonium salt) - Organization (1 ), R9 may be a divalent aliphatic group, an alicyclic group, or an aromatic group such as a methylene group, an ethylene group, a propylene group, a butylene group, an isobutylene group, a phenylene group, or a xylylene group; R
'2 is not only a hydrogen atom, but also a methyl group, an ethyl group,
Monovalent hydrocarbon groups such as propyl, phenyl, and benzyl groups can be mentioned.

Furthermore, in composition (III), examples of X- include inorganic anion species such as chlorine ion and sulfonate ion, and organic anion species such as carbonium ion and sulfonium ion.

Specific examples of the fbl component represented by the structure (I[I) include 2-methacryloyloxyethyltrimethylammonium, 2-acryloyloxyethyltrimethylammonium, 2-methacryloyloxyethyltriethylammonium, 2-acryloyloxyethyl Triethylammonium, 3-(N-methacryloyl)aminopropyltrimethylammonium, 3-(N-acryloyl)aminopropyltrimethylammonium, 3
A compound obtained from a combination of (N-methacryloyl)aminopropyltriethylammonium, 3-(N-acryloyl)aminopropyltriethylammonium, etc., and an inorganic or organic anion species; 2-methacryloyloxyethyldiethylammonioacetate, 2-Acryloyloxyethyldiethylammonioacetate, 3-(N-methacryloyl)aminopropyldimethylammonioacetate, 3-(N-methacryloyl)aminopropyldiethylammonioacetate, 3-(N-acryloyl)aminopropyldiethylammonioacetate Examples include compounds obtained from a combination of acetate, 2-methacryloyloxyethyldiethylammoniosulfate, 3-(N-methacryloyl)aminopropyldiethylammoniosulfate, and an inorganic or organic anion species.

Among these, 2-acryloyloxyethyltrimethylammonium chloride, 2-methacryloyloxyethyltrimethylammonium chloride, 3-( Particularly preferred are N-acryloyl)aminopropyltrimethylammonium chloride, 3-(N-methacryloyl)aminopropyltrimethylammonium chloride, 2-methacryloyloxyethyldiethylammonioacetate, 3-(N-acryloyl)aminopropyldiethylammonioacetate, and the like. .

These (bl components) can be used alone or in combination of two or more.

Furthermore, the (c1 component) is used for the purpose of controlling the solubility of the copolymer in the developer used when forming a pattern using the dyeable radiation-sensitive resin used in the present invention.

As this component (c), compounds represented by the following structure (IV) can be exemplified.

I3 (In the formula, RI3 represents a hydrogen atom or a methyl group, and RI4 represents an organic group having 1 to 8 carbon atoms.) RI in the above-mentioned structure (rV) constituting component (c)
The organic group having 1 to 8 carbon atoms which is 4 is, for example, a methyl group, a hexyl group, a heptyl group, an octyl group, a phenyl group, a 2-
Examples include ethylhexyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, and preferably a linear alkyl group.

Specific examples of tC) components include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl methacrylate, phenyl acrylate, phenyl methacrylate, and methacrylic acid. Hydroxyethyl, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate,
2-hydroxybutyl acrylate, 2-methacrylate
-Hydroxybutyl and the like.

These (c) components can be used alone or in combination of two or more.

The copolymerization ratio of component (a), component (b), and component (c1) used in the copolymer of the present invention is usually (al component: 30 to 94 mol%, preferably 60 to 80 mol%, ( b
l component is 5 to 60 mol%, preferably 10 to 30 mol%
, component (c) is 1 to 50 mol%, preferably 5 to 30 mol%.

(If the Al content is less than 30 mol%, resolution during pattern formation may decrease or film roughness may occur;
If it exceeds mol %, the proportion of component ('b) may decrease and the dyeability may deteriorate.

In addition, if the BL component is less than 5 mol%, the dyeability is low (and it is difficult to reduce the light transmittance at a film thickness of around 1 μm, while if it exceeds 60 mol%, the Al component and (
The molar ratio of the c1 component decreases, and resolution during pattern formation may decrease or film roughness may occur.

Furthermore, if component (c) is less than 1 mol %, resolution during pattern formation may decrease, while if it exceeds 50 mol %, film roughness is likely to occur.

In addition, in order to impart radiation sensitivity to the copolymer itself, a radiation-sensitive monomer such as 4'-methacryloyloxychalcone, 4'-acryloyloxychalcone, 4-methacryloyloxychalcone, 4- Acryloyloxychalcone, 4'-methacryloyloxy-4-methoxychalcone, 4'-axoloyloxy-4-methoxyalcone,
4-methacryloyl waxy 4'-methoxychalcone, 4
-acryloyloxy-4'-methoxychalcone, 4'-
Chalcone derivatives such as methacryloyloxy-4-nitrochalcone and 4'-acryloyloxy-4'-nitrochalcone can also be copolymerized.

Among these, 4'-methacryloyloxychalcone and 4'-methacryloyloxychalcone are preferred from the viewpoint of transparency in the visible light region and radiation sensitivity of the copolymer.

The copolymerization ratio of this radiation-sensitive monomer in the copolymer is usually 2 to 60 mol%, preferably 10 to 40 mol%.

The molecular weight of the copolymer used in the present invention is not particularly limited, but usually has a polystyrene equivalent weight average molecular weight of 5,000 to 1.000,000, preferably 10.000 to 500. It is .000.

Further, the polymerization form of the copolymer is not particularly limited, and may be either a random copolymer, a block copolymer, etc., and the polymerization method may be either solution polymerization, emulsion polymerization, etc., but solution polymerization is preferable. It is.

In this solution polymerization, fa) is added to a solvent that can dissolve the copolymer.
Components (c) and, if necessary, a radiation-sensitive monomer are mixed, dissolved, and polymerized using a polymerization initiator.

The solvent used in this polymerization is not particularly limited as long as it can dissolve the copolymer; specifically, water; alcohol solvents such as methanol and ethanol; cellosolve solvents such as methoxyethanol and ethoxyethanol; Diol solvents such as ethylene glycol and diethylene glycol; Ester solvents such as ethylene glycol methyl ether acetate and ethylene glycol ethyl ether acetate; N-methylpyrrolidone, NN-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, T-butyrolactone These can be used alone or in combination of two or more.

The weight ratio of the solvent to the monomer is usually 1/1 to 10/1, preferably 2/1 to 4/1.

Note that these solvents are also used as a solvent when the dyeable radiation-sensitive resin used in the present invention is made into a solution.

As the polymerization initiator, compounds that generate radicals, anions, or cations can be used, such as cumene hydroperoxide, t-butyl hydroperoxide, sodium naphthalene, trichloroacetic acid, trifluoroboron, azobisisobutyronitrile, etc. can be mentioned.

The molecular weight of the copolymer can be adjusted depending on the amount of the polymerization initiator used, and the amount used is usually 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of monomers to be copolymerized. be.

In addition, the polymerization temperature is usually 0 to 200°C, preferably 5°C.
It is 0-100°C.

Furthermore, a chain transfer agent or a polymerization inhibitor may be added to the polymerization system for the purpose of adjusting the molecular weight of the copolymer.

The dyeable radiation-sensitive resin used in the present invention can be used as it is, or by agro-condensing and diluting the copolymer solution obtained in this way. It is also possible to separate the combined product and redissolve it for use.

In the present invention, when the copolymer is not imparted with radiation sensitivity, a radiation-sensitive cross-linking agent is added to impart radiation-sensitivity to the copolymer. Examples of this radiation-sensitive cross-linking agent include bisazide. Examples include compounds.

Examples of the bisazide compound include 4,4'-diazidostilbene-2,2'-disulfonic acid, 4,4'-
Diazidohenzalacetophenone-2 sulfonic acid, 4.
Water-soluble bisazide compounds such as 4'-diazidostilhene α-carboxylic acid and their sodium salts, potassium salts, and ammonium salts; p-phenylenebisazide, 4
, 4'-diazidobenzophenone, 4,4'-diazidostilhene, 4,4'-diazidodiphenylmethane, 4
．． 4'-Diazidobenzalacetophenone, 2.6-bis-(4'-azidobenzal)cyclohexanone, 2,
such as 6-bis-(4'-azidohenzal)-4-methylcyclohexanone? Why? Mention may be made of soluble bisazide compounds.

The amount of the radiation-sensitive crosslinking agent to be added can be arbitrarily determined so long as the dyeable radiation-sensitive resin forms a coating film having solvent resistance and adhesive properties, but usually 0 to 100 parts by weight of the copolymer. .5 to 20 parts by weight, preferably 1 to 15 parts by weight; if it is less than 0.5 parts by weight, radiation crosslinking is difficult to occur, while if it is used in excess of 20 parts by weight, reactions between products decomposed by radiation occur. Furthermore, when formed into a coating film, the stability may be insufficient.

In addition, in the case of a copolymer obtained by copolymerizing the radiation-sensitive monomer, an angry radiation crosslinking agent can also be used in combination.

In addition, the dyeable radiation-sensitive resin used in the present invention includes:
Other additives may be added for the purpose of adjusting the viscosity of the resin, improving the coating properties, improving the adhesion of the coating film to the substrate, improving the flatness of the coating film, improving the development characteristics, etc.

Here, other additives include fillers, polymer compounds other than those mentioned above, surfactants, adhesion promoters, antioxidants,
Examples include ultraviolet absorbers, anti-aggregation agents, and sensitizers.

Specific examples of these additives include fillers such as glass and alumina; polyvinyl alcohol, polyacrylic acid,
Polymer compounds such as polyethylene glycol monoalkyl ether and polyfluoroalkyl acrylate; Nonionic, cationic, or anionic surfactants; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N- (2
aminoethyl) 3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropylmethyldimethoxysilane, 2
- Adhesion promotion of (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Agent; 2
, 2-thiobis(4-methyl 6-t-butylphenol), 2. ．． Antioxidants such as 6-di-t-butylphenol; UV absorbers such as 12-(3t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxyhensiphenon; sodium polyacrylate, Anti-aggregation agents such as sodium methacrylate; 2-dibenzoylmethylene 3-methyl-β-naphthothiazoline, N-phenylthioacridone, 4-(4
-amyloxyphenyl)-2,6-bis(4-methoxyphenyl)thiapyrylium perchlorate.

The viscosity of the dyeable radiation-sensitive resin solution obtained in this way varies depending on the molecular weight of the copolymer, the solvent used, etc., but is usually 20 to aoocps (at 25°C), preferably 50 to 200 cps (at 25°C). ).

In addition, the solid content concentration of the dyeable radiation-sensitive resin solution at this time is usually about 5 to 20% by weight.

Next, in the present invention, the dyeable radiation-sensitive resin thus obtained is used to coat a substrate with an arbitrary thickness by, for example, a spin coater method, a roll coater method, a screen printing method, a spray method, etc. For example, a coating film is formed to have a dry film thickness of 1 to 2 μm, and for example, a coating film is formed at 70 to 150°C for 10 to
Dry for about 30 minutes.

Here, the substrate on which the dyeable radiation-sensitive resin coating film used in the present invention is formed includes, for example, soda glass, Pyrex glass, quartz glass used in liquid crystal display elements, and transparent conductive films on these glasses. For example, a photoelectric conversion element substrate used in a solid-state image sensor, such as a silicon substrate, may be used.

Next, for example, 10 to 1
, 0OOITIJ/-, and then developed with a developer.

Here, examples of the developer include water; methanol, ethanol, propatool, isoproptool, butanol, isobutanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, Examples include alcohol solvents such as diethylene glycol monoethyl ether and diethylene glycol monobutyl ether.

The development is carried out for about 1 to 5 minutes each by a method such as depupping or spraying. After these steps, it is usually heated at 100 to 180°C for 15 minutes to dry the coating sufficiently.
Dry for about 60 minutes.

Next, the dye used to dye the pattern formed in this way is an azo acid dye containing a metal complex salt, such as green dye, blue dye, red dye, black dye, etc. can be mentioned. Among these, black dye in particular can provide sufficient light shielding with a thin film.
Suitable for forming black stripes.

Examples of the azo acidic black dye include Lanasinbra Tsuku BRL (manufactured by Mitsubishi Kasei), Kayakaran Black 2RL (specially manufactured by Nippon Kayaku), Blank 181 (manufactured by Nippon Kayaku), and Black 205 (manufactured by Nippon Kayaku). ), but the copper complex dyes Black 181 and Black 205 are particularly preferred in terms of heat resistance.

Among azo acidic black dyes, those that do not have metal complex salts in their structure have low dyeing properties, so
It is difficult to sufficiently block light with thin films.

Dyeing using this azo acidic black dye is carried out, for example, from 0.01 to 10% by weight, preferably from 0.1 to 2% by weight of the dye.
The substrate having the pattern formed as described above is placed in an aqueous solution of 5 to 95°C, preferably 40 to 80°C.
This can be done by soaking for about 1 to 30 minutes, washing with water, and then drying.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited thereto.

In the examples, parts and percentages refer to weight M unless otherwise specified.
It is a standard.

Example I 60 parts of N-vinyl-2-pyrrolidone, 2-meta/) I
J To 10 parts of a copolymer consisting of 20 parts of loyloxyethyltrimethylammonium chloride and 20 parts of methyl methacrylate, 4,4'-diazidostilbene-2,2
0.5 parts of sodium '-disulfonate and 89.5 parts of methyl cellosolve were mixed and dissolved to prepare a dyeable radiation-sensitive resin solution.

This dyeable radiation-sensitive resin solution was applied to a glass plate using a spin coater so that the dry film thickness was 1IJm, and after drying at 140°C for 30 minutes, it was applied through a mask with a predetermined pattern. The film was developed by irradiating it with 40 mJ/ci ultraviolet light and immersing it in ultrapure water for 1 minute.
Obtained a predetermined pattern.

This glass plate was dried at 180°C for 30 minutes, and then dyed with a 0.5% aqueous solution of Black 181 (manufactured by Nippon Kayaku ■, azo acidic black dye) at 70°C for 10 minutes to form a black pattern. A glass plate was obtained.

The film thickness of the obtained black pattern was 1.2 μm, and the light transmittance of the black pattern from 400 to 700 nm was all 1.
% or less.

Furthermore, there was no film roughness or pattern collapse of the black pattern, and the pattern had an excellent shape.

Comparative Example 1 A solution of gelatin and ammonium dichromate was used instead of the dyeable radiation-sensitive resin of Example 1, and a glass plate was coated in the same manner as in Example 1 so that the dry film thickness was 1 μm. , dried and then exposed to < 100 m J
/ctA ultraviolet vA)L, developed (immersed in ultrapure water for 1 minute), dried (150"C for 130 minutes), and dyed under the same conditions as in Example 1 to obtain a black pattern.

The film thickness of the obtained black pattern was 1.1 μm, and the light transmittance of the black pattern in the range of 400 to 700 nm was 20 to 700 nm.
It was 70%.

Comparative Example 2 A black pattern was obtained in the same manner as in Comparative Example 1, using a solution in which casein and ammonium dichromate were dissolved instead of the dyeable radiation-sensitive resin of Example 1.

The film thickness of the obtained black pattern was 1.1 μm, and the light transmittance of the black pattern in the range of 400 to 700 nm was 20 to 700 nm.
It was 70%.

Example 2 A black pattern was obtained in the same manner as in Example 1, except that Blank 205 (manufactured by Nippon Kayaku ■, azo acidic black dye) was used instead of Black 181.

The film thickness of the obtained black pattern was 1.2 μm, and the light transmittance of the black pattern in the wavelength range of 400 to 700 nm was 1% or less.

Example 3 To 10 parts of a copolymer consisting of 50 parts of N-vinyl-2-pyrrolidone, 30 parts of 3-(N-methacryloyl)aminopropyltrimethylammonium chloride, and 20 parts of ethyl acrylate, 0 parts of 4,4'diazide chalcone was added. .5 parts and 89.5 parts of ethyl cellosolve were mixed and dissolved to prepare a dyeable radiation-sensitive resin solution.

Using this dyeable radiation-sensitive resin solution, a black pattern was obtained in the same manner as in Example 1.

The thickness of the obtained black pattern was 1.0 lum, and the light transmittance of the black pattern from 400 to 700 nm was 1% or less.

〔Effect of the invention〕

Although the present invention forms a colored pattern by dyeing a pattern made of a dyeable material, it has high dyeability even when the film thickness is around 1 μm, and it has a high dyeability compared to conventional dyeable materials such as gelatin and casein. It is possible to improve the quality of color separation filters, which was not possible with optical materials, and in particular, by dyeing them black, it becomes possible to form black stripes with excellent light-shielding properties.

Patent applicant: Japan Synthetic Rubber Co., Ltd. Agent: Patent attorney Takashi Shirai

Claims (1)

[Claims] (1) A copolymer with (a) vinyl lactams, (b) a monomer having a quaternary amine structure and a polymerizable unsaturated bond, and (c) a (meth)acrylic acid ester. Applying the dyeable radiation-sensitive resin containing the dye to the substrate,
After irradiating with radiation and developing to form a pattern,
A method for forming a colored pattern by dyeing with an azo acid dye containing a metal complex salt.