JP3445194B2 - Photosensitive composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive composition, and more particularly to a photosensitive composition having extremely high resolution and a color cathode ray tube using the same.

[0002]

2. Description of the Related Art Usually, for example, for a black matrix of a color cathode ray tube, a water-soluble photosensitive composition is applied to the entire surface of a glass panel; and after exposing the exposed portion to water by exposing it to ultraviolet rays through a photomask; It is produced by removing the unexposed part by spraying to form a resist pattern; applying a black component dispersion liquid such as graphite; decomposing the resist pattern with an oxidizing agent; removing the decomposed product with a water spray; . Conventionally, as a photosensitive composition used in the process, for example, (1) a photosensitive composition comprising polyvinylpyrrolidone and a water-soluble azide compound (Japanese Patent Application Laid-Open No. Sho 4)
No. 8-79970), (2) a photosensitive composition comprising an acrylamide-diacetone acrylamide copolymer and a water-soluble azide compound (Japanese Patent Laid-Open No. 50-33764).
Have been proposed.

[0003]

However, since the above-mentioned photosensitive compositions (1) and (2) do not have sufficient resolution, it is difficult to produce a high-definition cathode ray tube, and the production of a cathode ray tube is difficult. There was a problem that deteriorated the sex.

[0004]

Means for Solving the Problems The inventors of the present invention have made earnest studies to solve the problems of the conventional photosensitive composition for forming a black matrix of a color CRT, and as a result, as a photosensitive composition, an aqueous solution was prepared. The inventors have found that a composition using a water-soluble polymer, a water-soluble azide compound, and a water-soluble vinyl-based monomer having a specific functional group has extremely high resolution, and arrived at the present invention.

That is, the present invention comprises 20 to 89% by weight of a water-soluble vinyl polymer (A) and a water-soluble azide compound (B).
1 to 30% by weight and one vinyl group selected from the group consisting of an aromatic ring-containing water-soluble monomer, a heterocyclic ring-containing water-soluble monomer and an acrylic water-soluble monomer having a molecular weight of 130 or more.
One or more water-soluble vinyl monomers (C) 10 to 80
%, And a color cathode ray tube formed by using the photosensitive composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the composition of the present invention, the water-soluble vinyl polymer (A) is not particularly limited,
For example, N-vinylformamide (co) polymer, N-vinylacetamide (co) polymer, (meth) acrylamide (co) polymer, N-alkyl (meth) acrylamide having an alkyl group having 1 to 5 carbon atoms, An N, N-dialkyl (meth) acrylamide whose alkyl group has 1 to 5 carbon atoms,
(Meth) acrylamide-diacetone (meth) acrylamide copolymer, polyvinyl alcohol (co) polymer,
Examples thereof include (meth) acrylic acid (co) polymers and polyvinylpyrrolidone (co) polymers. Of these, N-vinylformamide (co) polymer and N-vinylacetamide (co) polymer are preferable from the viewpoint of sensitivity and patterning property.

Weight average molecular weight of (A) (Measurement method: GPC
Method) is usually 50,000 or more, preferably 5
20,000 to 2,000,000, more preferably 2
It is from 0,000 to 1,500,000.

The blending ratio of (A) is usually 20 to 89% by mass, preferably 30 to 8% by mass based on the mass of the photosensitive composition.
It is 0 mass%. If (A) is less than 20% by mass, the adhesion to the glass surface will be poor, and if it exceeds 89% by mass, the resolution will be poor.

The water-soluble azide compound (B) used in the composition of the present invention is not particularly limited as long as it is a compound capable of forming nitrene upon irradiation with ultraviolet rays and reacting with the above (A). Water-soluble aromatic bisazide compounds having two azide groups are preferred. As a specific example, a sulfonic acid group-containing water-soluble azide compound [4,4′-diazidostilbene-2,2′-disulfonic acid, 4,4 ′
-Diazidobenzal acetophenone-2-sulfonic acid,
1,5-pent-3-one-1,4-diethenyl-bis (azidobenzenesulfonic acid), 2,6-bis (4-azidobenzal-2-sulfonic acid) -cyclopentanone, etc.], containing carboxylic acid group Examples thereof include water-soluble azide compounds [4,4′-diazidostilbene-α-carboxylic acid and the like] and the above salts (organic amine salts, alkali metal salts, alkaline earth metal salts and the like) and the like.

(B) may be used alone or as a mixture of two or more kinds. Among these, the sulfonic acid (salt) group-containing water-soluble azide compound is preferable from the viewpoint of solubility, and the particularly preferable one is sodium 4,4′-diazidostilbene-2,2′-disulfonate.

The blending ratio of (B) is usually 1 to 30% by mass, preferably 1 to 20% by mass, based on the mass of the photosensitive composition. If (B) is less than 1% by mass, the sensitivity will be poor, and if it exceeds 30% by mass, the adhesion to the glass surface will be poor.

The water-soluble vinyl monomer (C) used in the composition of the present invention includes an aromatic ring-containing water-soluble monomer, a heterocyclic ring-containing water-soluble monomer and a molecular weight of 130 or more, preferably a molecular weight of 130. To one or more water-soluble vinyl monomers selected from the group consisting of ˜500 acrylic water-soluble monomers. Specific examples thereof include an aromatic ring-containing water-soluble monomer [styrene sulfonic acid or its salt (amine salt, alkali metal salt, etc.), vinylbenzyltrimethylammonium hydroxide, etc.]; Imidazole, vinylpyridine, N-vinylpyrrolidone, N- (meth) acryloylmorpholine, N-((meth) acryloyloxy) ethylmorpholine, etc.]; Acrylic water-soluble monomer having a molecular weight of 130 or more (preferably 130 to 500) (1) Acrylamide-based monomer [N-alkyl (meth) acrylamide [N- whose alkyl group has 5 to 10 carbon atoms]
Pentyl (meth) acrylamide, etc.], an alkyl group having 3 to 7 carbon atoms, N, N-dialkyl (meth) acrylamide [N, N-diisopropyl (meth) acrylamide, etc.], and an alkyl group having 1 to 5 carbon atoms. N, N, -dialkylaminoethyl (meth) acrylamide [N,
N, -dimethylaminoethyl (meth) acrylamide,
N, N, -diethylaminoethyl (meth) acrylamide, etc.], N, N, -dialkylaminopropyl (meth) acrylamide having an alkyl group having 1 to 5 carbon atoms [N,
N, -dimethylaminopropyl (meth) acrylamide, N, N, -diethylaminopropyl (meth) acrylamide, etc.], N-alkyloxymethyl (meth) acrylamide having an alkyl group having 3 to 7 carbon atoms [N-isopropyloxymethyl (Meth) acrylamide, N-butyloxymethyl (meth) acrylamide, etc.], diacetone (meth) acrylamide, etc.]; (2) Acrylate-based monomer [hydroxyl or alkoxy group-containing (meth) acrylic acid ester, for example, 2-hydroxy Ethyl methacrylate, alkyl group having 3 to 3 carbon atoms
7 hydroxyalkyl (meth) acrylates [2-hydroxypropyl (meth) acrylate, etc.], glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate and other hydroxyl group-containing (meth) acrylates; 1 to 4) ether, such as 2-ethoxyethyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, carbitol (meth) acrylate, etc.]; (3) Sulfonic acid (salt) group-containing monomer [2 -(Meth) acrylamido-2-methylpropanesulfonic acid, 3-sulfopropyl (meth) acrylate, or salts thereof (amine salts, alkali metal salts, etc.)]; (4) Phosphoric acid (salt) group-containing unit amount Body [[2-((meth) acryloyloxy) ethyl] And salts thereof (such as amine salts and alkali metal salts)]; (5) quaternary ammonium salt group-containing monomer [[2-((meth) acryloyloxy) ethyl] trimethylammonium chloride etc.]; Can be mentioned.

(C) may be used alone or as a mixture of two or more kinds. Among these, acrylic water-soluble monomers having a molecular weight of 130 or more are preferred from the viewpoint of resolution, particularly preferred are acrylamide monomers having a molecular weight of 130 or more, and more preferred are diacetone acrylamide. .

The blending ratio of (C) is usually 10 to 80% by mass, preferably 15 to 6 based on the mass of the photosensitive composition.
It is 0 mass%. If the content of (C) is less than 10% by mass, the resolution will be poor, and if it exceeds 80% by mass, the sensitivity will be poor.

Since the composition of the present invention contains (C), it exhibits reciprocity law failure characteristics, resulting in a composition having high resolution. The reciprocity law failure property is a property of forming a stripe or dot pattern having a substantially smaller area than the light irradiation area on the glass surface in the presence of gaseous oxygen. Regarding the reciprocity law failure characteristic, JP-A-48-79970, Po,
ly. Eng. Sci., 17 (6), 353 (1977). By using a photosensitive composition exhibiting reciprocity law failure for forming a black matrix of a color cathode ray tube, a black matrix having an area smaller than the mask area can be formed. When green, blue, and red phosphor patterns are sequentially formed on the black matrix-formed panel thus formed, the area of the phosphor pattern also becomes substantially smaller than the mask area. Therefore, if a color cathode ray tube is created using this mask, the size of the electron beam irradiated through the slits or small holes of the mask will be larger than the phosphor pattern, so the obtained color cathode ray tube will be bright and have a high contrast. Will be excellent. That is, in order to produce a high-definition and high-quality color cathode ray tube, it is essential to form a black matrix using a photosensitive composition that exhibits reciprocity law failure characteristics.

In order to exhibit the reciprocity law failure characteristic, it is necessary that gaseous oxygen be present in the vicinity of the azide compound as described above, and for that purpose, the photosensitive composition coating film must have oxygen permeability. There is. The photosensitive composition of the present invention polymerizes (C) at the time of light irradiation, as a result, the permeability of gaseous oxygen of the photosensitive composition coating film is enhanced, and reciprocity law failure is exhibited.
As a result, the photosensitive composition has high resolution. Also,
When (A) is a polymer having a repeating unit derived from (C), the photosensitive composition comprising (A) and (B) exhibits reciprocity failure characteristics, but by incorporating (C) ,
Further, the reciprocity law failure characteristic is enhanced, and as a result, the resolution can be further enhanced.

The composition may optionally contain an adhesion improver (D). By including (D), the adhesion to glass can be improved. Examples of (D) include silane coupling agents, titanium-based coupling agents, organic carboxylic acid-based compounds, organic phosphoric acid-based compounds, organic phosphoric acid ester-based compounds, and the like, preferably silane coupling agents [eg vinyl. -Tris- (β-methoxyethoxy) silane, N-β
-(Aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl)
-Γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxy Propylmethyldiethoxysilane and the like] and titanium-based coupling agents [for example, dihydroxy-bis (lactado) titanium, dialkyl-bis (triethanolaminato) titanium, oxotitanium bis (monoammonium oxalate, etc.) (D).
In the case of containing, the compounding amount is usually 10 mass% or less, preferably 0.01 to 5 mass% with respect to the mass of (A).
Is.

The photosensitive composition of the present invention may contain a water-soluble solvent as a diluent. By including a diluent, it becomes possible to control the coating property, storage stability, developing property, adhesiveness, etc. of the composition. The diluent is not particularly limited as long as it is compatible with each component, for example, water; alcohol solvents such as methanol, ethyl alcohol, isopropyl alcohol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol monoether. Glycol ether solvent such as ethyl ether;
Examples thereof include amide solvents such as N-methylpyrrolidone, 2-pyrrolidone, dimethylformamide and N, N-dimethylacetamide.

Among these, water and glycol ether type solvents are preferable, and water is particularly preferable from the viewpoint of sensitivity and resolution. The blending amount of the diluent can be arbitrarily set depending on the coating conditions of the photosensitive composition and the like,
2 to 100 times the mass of (A), preferably 5 to 7
It is 0 times.

If necessary, the composition of the present invention may contain a low molecular weight compound having a molecular weight of 990 or less, which contains a hydroxyl group and / or an iodine atom in the molecule. By including the low molecular weight compound, the developing characteristics, the adhesiveness, etc. can be adjusted, and the sensitivity can be further improved. Examples of the low molecular weight compound having a hydroxyl group in the molecule include n-butanol, ethylene glycol, diethylene glycol, propylene glycol,
1,3-butylene glycol, 1,5-pentanediol, triethanolamine, glycerin, erythritol, pentaerythritol, sorbitol, hexitol and the like can be mentioned.

Examples of the low molecular weight compound containing an iodine atom in the molecule include iodoacetic acid and 3,5-diamino-
2,4,6-triiodobenzoic acid, 3,5-diamino-
Sodium 2,4,6-triiodobenzoate, 3-amino-2,4,6-triiodobenzoic acid, 3-amino-
Sodium 2,4,6-triiodobenzoate, 5-amino-2,4,6-triiodoisophthalic acid, sodium 5-amino-2,4,6-triiodoisophthalate, 5
-Amino-2,4,6-triiodoisophthalamic acid,
Sodium 5-amino-2,4,6-triiodoisophthalamate, 3,5-diiodosalicylic acid, sodium 3,5-diiodosalicylate, 2,3,5-triiodobenzoic acid, 2,3,5 -Sodium triiodobenzoate, tetraalkylammonium iodide, sodium iodide, potassium iodide and the like.

When a low-molecular compound containing a hydroxyl group and / or an iodine atom is contained in the above-mentioned molecule, the compounding amount thereof is 1 to 100% by mass based on the mass of (A) from the viewpoint of addition effect and developability. , Preferably 1 to 50% by mass.

Further, the composition of the present invention may contain a surfactant, if necessary, in order to improve the wettability with respect to the substrate. The surfactant is not particularly limited as long as it is compatible with each component, and examples thereof include an anionic surfactant, a nonionic surfactant, and a cationic surfactant. Among these, nonionic surfactants (eg, sorbitan ester ethylene oxide adducts, alkylphenol ethylene oxide adducts, etc.) are preferable from the viewpoint of stability. When a surfactant is contained, its content is 0.01 to 5% by mass, preferably 0.05 to 3% by mass based on the mass of (A) from the viewpoint of the effect of addition and the developability.

As a specific example using the composition of the present invention, the formation of a black matrix of a color CRT will be described below. Examples of the method for forming a black matrix of a color CRT include a photosensitive composition of the present invention containing a water-soluble vinyl polymer (A), a water-soluble azide compound (B) and a water-soluble vinyl monomer (C). , Usually 0.1-2μ on glass panel
Coating with a film thickness of m; drying with a hot plate, infrared heater, far-infrared heater, etc. to form a coating film; through a photomask having a desired pattern, ultra-high pressure mercury lamp, high pressure mercury lamp, metal halide lamp, etc. Usually exposed to an illuminance of 0.5 to 50 mJ / cm ² ; developed with water to wash and remove the unexposed portion to form a resist pattern; apply a black component dispersion liquid such as graphite; hot plate, infrared ray An example is a method of performing a series of steps of drying with a heater, a far infrared heater or the like; oxidizing and decomposing the resist pattern with an oxidizing agent such as hydrogen peroxide; and developing with water.

Further, since the photosensitive composition of the present invention has reciprocity law failure property, the ultraviolet exposure illuminance in the above step is preferably in the range of 0.02 to 1 mW / cm ² . When the exposure illuminance is below 0.02 mW / cm ² ,
The pattern obtained by UV irradiation may be extremely small or the pattern may not be formed. If the exposure illuminance exceeds 1 mW / cm ² , the exposure time for obtaining a pattern of an appropriate size will be extremely short, and as a result , Pattern swelling and wrinkling may occur.

Since the photosensitive composition of the present invention has extremely high resolution, it is not only used for forming a black matrix of a color cathode ray tube, but also as a phosphor resist for a color cathode ray tube, an etching resist for forming a shadow mask, a resist for an inner surface filter of a color cathode ray tube. , Color filter black matrix forming resist, color filter pigment dispersion resist, printed wiring board solder resist, printed wiring board etching resist, printed wiring board dry film resist, interlayer insulating material, liquid crystal transparent conductive film (ITO) It is also extremely useful for patterning resists, photosensitive printing plates, printing inks, photocurable coating materials, and the like.

[0027]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the following, "part" means "part by mass" and "%" means "% by mass". The “exposure” in this embodiment means exposure with a gap of 5.0 mm kept between the photomask and the glass substrate, that is, gap exposure.

Example 1 A photosensitive composition (1) of the present invention was obtained by the following formulation. The composition (1) was applied on a glass substrate by a spin coating method so as to have a film thickness of 0.5 μm, and dried on a hot plate at 50 ° C. for 1 minute to form a coating film. This coating film was used as a photomask in a sharpness test chart No. 1 using an ultra-high pressure mercury lamp. 1 [made by Toppan Printing Co., Ltd.]
After performing an exposure amount of 2.5 mJ / cm ² using
It was developed with water at room temperature to form a resist pattern. The composition exhibited outstanding reciprocity failure characteristics. Graphite dispersion "Electrodag ED-1530" (manufactured by Nippon Acheson Co., Ltd.) on the entire surface of the glass substrate on which this pattern is formed.
The graphite film thickness is 0.8μ by spin coating.
It was applied so that it would be m. Further, the graphite-treated glass substrate is dipped in an etching solution containing 3% hydrogen peroxide and 0.5% sulfuric acid at room temperature for 30 seconds and developed with water at room temperature to form a target black matrix. , The resolution in the black matrix was measured. The resolution was 12 μm. [Prescription of Photosensitive Composition (1)] 30% aqueous solution of polyvinyl formamide [Mitsubishi Chemical Corporation's "PNVF": weight average molecular weight = 100,000] 33 parts 4,4'-diazidostilbene-2,2 ' -Sodium disulfonate 0.7 parts Diacetone acrylamide 2.5 parts Surfactant [NONION LT-221 manufactured by NOF CORPORATION] 0.04 parts N-β- (aminoethyl) -γ-aminopropyltri Methoxysilane 0.08 parts Ion-exchanged water 150 parts

Example 2 A photosensitive composition (2) of the present invention was obtained according to the following formulation. The composition (2) was applied on a glass substrate by the same method as in Example 1, dried, exposed, developed, coated with a graphite dispersion solution, etched, and developed, and the resolution in a black matrix was measured. It was 14 μm.
Further, the composition exhibited remarkable reciprocity law failure characteristics. Polyvinyl acetamide 40% aqueous solution of [Showa Denko KK "GE-191LL": weight average molecular weight = 40,000] [Formulation of photosensitive composition (2)] 25 parts of 4,4'-diazidostilbene -2 , 2'-sodium disulfonate 0.7 parts Diacetone acrylamide 2.5 parts Surfactant [NONION LT-221 manufactured by NOF CORPORATION] 0.04 parts N-β- (aminoethyl) -γ- Aminopropyltrimethoxysilane 0.08 parts Ion-exchanged water 150 parts

Comparative Example 1 A comparative photosensitive composition (ratio 1) was obtained according to the formulation shown below. When the composition (ratio 1) was applied on a glass substrate, dried, exposed, developed, coated with a graphite dispersion solution, etched, and developed in the same manner as in Example 1, the resolution in a black matrix was measured. , 25 μm. Moreover, this composition showed the characteristic of reciprocity law, and did not show the characteristic of reciprocity law failure. [Prescription of Comparative Photosensitive Composition (1)] 30% aqueous solution of polyvinylformamide [Mitsubishi KK-made "PNVF": weight average molecular weight = 100,000] 33 parts 4,4'-diazidostilbene-2, Sodium 2'-disulfonate 0.7 part Surfactant [NONION LT-221 manufactured by NOF CORPORATION] 0.04 part N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.08 Part Ion-exchanged water 150 parts

[0031]

The photosensitive composition of the present invention has the following effects and is extremely useful. 1) The photosensitive composition of the present invention has high resolution because it exhibits reciprocity law failure characteristics. Therefore, when the photosensitive composition is used for forming a black matrix of a color CRT, a black matrix excellent in contrast is formed, so that a high-definition and high-quality color CRT can be produced. 2) Since it does not contain chromium compounds, which are harmful substances, it is not necessary to equip equipment for removing chromium in wastewater, and environmental pollution does not occur.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08K 5/28 C08K 5/28 5/42 5/42 C08L 29/04 C08L 29/04 A 33/02 33/02 33/26 33/26 39/02 39/02 39/06 39/06 G03F 7/027 G03F 7/027 7/033 7/033 (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00- 7/42

Claims (7)

(57) [Claims] 1. Water-soluble vinyl polymer (A) 20-89
% By weight, and 1 to 30% by weight of water-soluble azide compound (B)
And a vinyl group having one vinyl group selected from the group consisting of an aromatic ring-containing water-soluble monomer, a heterocyclic ring-containing water-soluble monomer, and an acrylic water-soluble monomer having a molecular weight of 130 or more.
A photosensitive composition comprising at least one (C) of 10 to 80% by mass of a vinyl monomer . 2. The composition according to claim 1, wherein the monomer (C) is diacetone acrylamide. 3. The polymer (A) is an N-vinylformamide (co) polymer, an N-vinylacetamide (co) polymer, a (meth) acrylamide (co) polymer, and an alkyl group having 1 carbon atom. To N-alkyl (meth) acrylamide, N-dialkyl (meth) acrylamide having 1 to 5 carbon atoms in the alkyl group, (meth) acrylamide-diacetone (meth) acrylamide copolymer, polyvinyl alcohol (co) The composition according to claim 1 or 2, which is one or more polymers selected from the group consisting of polymers, (meth) acrylic acid (co) polymers and polyvinylpyrrolidone (co) polymers. 4. The azide compound (B) is one or more azide compounds selected from the group consisting of sulfonic acid (salt) group-containing azido compounds and carboxylic acid (salt) group-containing azido compounds. The composition according to any one of 1. 5. The composition according to claim 1, further comprising 0.01 to 10% by mass of the adhesion improver (D) with respect to the mass of the polymer (A). 6. The composition according to claim 1, which is used for forming a black matrix of a color cathode ray tube. 7. A color cathode ray tube formed by using the composition according to claim 6.