JPH08339078A - Photosensitive composition and pattern forming method using that - Google Patents

Abstract

PURPOSE: To obtain a black matrix for a color CRT showing good contrast with good productivity by combining a water-soluble polymer, a cellulose deriv. having quaternary nitrogen and a water-soluble azide compd. CONSTITUTION: This photosensitive compsn. is prepared by dissolving or dispersing a water-soluble polymer, a cellulose deriv. having quaternary nitrogen, and a water-soluble azide compd. and if necessary, various compounding agents in a solvent essentially comprising water. The water-soluble polymer used is, for example, a polymer having a film-forming property such as polyvinyl pyrrolidone. The water-soluble azide compd. is, for example, a compd. expressed by formula. The cellulose deriv. having quaternary nitrogen is produced by the method described in US Pat. 2623042 or in Japan Pat. 45-20318. Thereby, the obtd. photosensitive compsn. is improved in various drawbacks of conventional photosensitive compsns., and a pattern forming method using the obtd. photosensitive compsn. is obtd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition and a pattern forming method, and more particularly to a photosensitive composition and a pattern forming method suitable for preparing a black matrix of a color cathode ray tube.

[0002]

2. Description of the Related Art A color cathode ray tube has a structure in which a stripe or dot pattern made of phosphors of red, green, and blue and its voids are filled with a non-emissive light-absorbing substance such as graphite on the inner surface of a face plate. The non-emissive light absorbing part filling the voids of the pattern is called a black matrix.

Here, the black matrix is generally prepared as follows. Apply the water-based photosensitive composition to the inner surface of the face plate, pass through the shadow mask to red,
A portion corresponding to the positions of the green and blue phosphor patterns is exposed and developed with water to obtain a pattern of the water-based photosensitive composition. Then, by applying a dispersion of graphite, by dipping the aqueous photosensitive composition in a degradable stripping solution to strip the aqueous photosensitive composition pattern and the graphite adhered on it together, the black matrix Created.

Conventionally, the following water-based photosensitive compositions (1) to (3) have been used for preparing this black matrix. (1) Polyvinyl alcohol-dichromate (2) Polyvinylpyrrolidone-water-soluble azide compound disclosed in JP-A-48-90185 (3) JP-B-52-20225 and the like Acrylamide-diacetone acrylamide copolymer-water-soluble azide compound, etc.

[0005]

However, conventionally used water-based photosensitive compositions have the following problems. The photosensitive composition of the above (1) has good sensitivity, good graphite releasability, etc., but poor resolution and stability over time, and has the problem of hexavalent chromium pollution. Above (2)
The photosensitive composition of (1) has good resolution and graphite releasability, but has a problem of poor adhesion to a glass substrate. Further, there is a drawback that the sensitivity is changed due to changes in humidity, temperature and the like, resulting in poor production stability. Above (3)
The photosensitive composition of (1) has good sensitivity, resolution, etc., but has a problem of poor adhesion to a glass substrate, like the photosensitive composition of (2).

Further, the present inventors have found that a photosensitive composition comprising N, N-dimethylacrylamide, a copolymer comprising acrylamide and a water-soluble azide compound has excellent sensitivity, resolution and releasability. However, similar to the photosensitive compositions of the above (2) and (3), it still has a problem of poor adhesiveness.

In order to improve the adhesion of a photosensitive composition comprising these water-soluble polymer and water-soluble azide compound to a glass substrate, these photosensitive compositions have hitherto been used as adhesion promoters, so-called silane coupling agents. Are used in combination. Here, if the silane coupling agent is omitted,
There is a problem that the adhesiveness to the glass substrate is too poor and the pattern is liable to peel during development. Therefore, conventionally, a photosensitive composition containing a silane coupling agent is always used. However, a photosensitive composition containing a silane coupling agent has poor stability over time,
There are problems that the adhesiveness is lowered at room temperature for about one week, and the aqueous solution of the photosensitive composition becomes cloudy.

It is an object of the present invention to provide a photosensitive composition in which various drawbacks of the conventional photosensitive composition described above are improved and a pattern forming method using the same.

[0009]

The above object can be achieved by combining a water-soluble polymer with a cellulose derivative having a quaternary nitrogen and a water-soluble azide compound. That is,
Although the present inventors have found that a photosensitive composition containing only a water-soluble polymer and a water-soluble azide has poor adhesiveness to a glass plate, the sensitivity can be improved by adding a cellulose derivative having a quaternary nitrogen to this photosensitive composition. It was found that the adhesiveness was improved as the amount was increased, and the present invention was completed based on this.

The composition of the photosensitive composition according to the present invention based on the above findings is characterized by comprising a water-soluble polymer, a quaternary nitrogen-containing cellulose derivative and a water-soluble azide compound.

In the above photosensitive composition, the weight ratio of the water-soluble polymer to the cellulose derivative having quaternary nitrogen is 1 for the water-soluble polymer and 0. It is characterized in that it is in the range of 001 to 0.2.

In the above photosensitive composition, the content of the quaternary nitrogen in the cellulose derivative having the quaternary nitrogen is 0.5 to 5% by weight.

In the above-mentioned photosensitive composition, the water-soluble azide compound is in the range of 2 to 50% by weight based on the total weight of the water-soluble polymer and the quaternary nitrogen-containing cellulose derivative. .

In the above photosensitive composition, the water-soluble polymer is polyvinylpyrrolidone having a K value of 30 or more.

In the photosensitive composition, the water-soluble polymer has a molar ratio of monomers of diacetone acrylamide and acrylamide such that the diacetone acrylamide is 1 and the acrylamide is 1.5 to 4.
It is a copolymer in the range of 0.

In the photosensitive composition, the water-soluble polymer has a molar ratio of N, N-dimethylacrylamide and acrylamide monomers, and the dimethylacrylamide is 1 to the acrylamide of 0.05 to 0.05.
It is characterized by being a copolymer in the range of 4.0.

In the above-mentioned photosensitive composition, a salt is contained in the range of 0.1% to 20% by weight based on the total weight of the water-soluble polymer, the quaternary nitrogen-containing cellulose derivative and the water-soluble azide compound. It is characterized by

In the above photosensitive composition, the salt contained is a tetraalkylammonium salt.

On the other hand, the pattern forming method according to the present invention comprises the steps of applying the photosensitive composition onto a substrate to form a coating film, and exposing the coating film of the photosensitive composition to a desired pattern. And a step of developing the pattern-exposed coating film of the photosensitive composition with water or an aqueous developer.

In the pattern forming method, the substrate on which the pattern is to be formed is the inner surface of the face plate of the color CRT.

The contents of the present invention will be described in detail below.

The composition of the photosensitive composition according to the present invention comprises a water-soluble polymer, a quaternary nitrogen-containing cellulose derivative and a water-soluble azide compound. The weight ratio of the water-soluble polymer to the water-soluble polymer is 1 to the weight ratio of the quaternary nitrogen-containing cellulose derivative to 0.001 to 0.2 of the quaternary nitrogen-containing cellulose derivative. preferable.
As a result, the obtained photosensitive composition has significantly improved adhesiveness and exhibits adhesiveness equivalent to that when a silane coupling agent is used.

Here, while the water-soluble polymer is 1, the cellulose derivative having quaternary nitrogen is 0.001 to 0.
The range of 2 is defined because when the ratio of the cellulose derivative having quaternary nitrogen is 0.001 or less, the effect of addition is small and the adhesiveness is insufficient, which is not preferable. On the other hand, when it is added in an amount of 0.2 or more, the viscosity of the photosensitive composition is too high, which is not preferable as a photosensitive composition for producing a black matrix of a color CRT.

As the water-soluble polymer used in the composition of the present invention, a water-soluble polymer capable of forming a film is used. Examples of such water-soluble polymers include polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, copolymers of vinyl alcohol and vinylpyrrolidone,
Copolymers of (meth) acrylamide and (meth) acrylate (JP-A-51-191033, JP-A-51-10)
3502, JP-A-63-10152), a copolymer of acrylamide (hereinafter referred to as "AA") and diacetone acrylamide (hereinafter referred to as DAA) (refer to JP-A-49-68801), grafted polyvinyl. Examples include polyvinyl alcohol resins containing alcohol, acetoacetate groups or allyl groups (see JP-A-58-174942), or copolymers of AA and N, N-dimethylacrylamide (hereinafter referred to as "DMAA"). be able to.

Among these water-soluble polymers, polyvinylpyrrolidone, a copolymer of AA and DAA, a copolymer of AA and DMAA and the like are preferable in terms of sensitivity and resolution. Here, the polyvinylpyrrolidone is commercially available, and any grade can be used, but it is particularly preferable that the K value is 30 or more from the viewpoint of sensitivity. The K value is a constant representing the degree of polymerization proposed by the German chemist Fikencher (Cellulosechemie 13 (1932), 56-64 and 71.
-74).

The copolymer of AA and DAA has a molar ratio of monomers of 1 to DAA and 1.5 to AA.
Copolymers in the range of 4.0 are preferred. This is the above AA
Is 1.5 or less, the oxygen permeability of the copolymer is too high, and the nitrene generated by exposure of the azide compound is easily quenched by oxygen. This is because the crosslinking reaction does not proceed, resulting in low sensitivity. On the other hand, when the AA exceeds 4.0, the viscosity of the copolymer becomes too high and the coating property tends to deteriorate. Further, generally speaking, the light passing through the shard mask spreads wider than the mask width of the shadow mask, but even if the spread light having low energy has low oxygen permeability in the film, it is easily photocured, As a result, there is also a problem that the resolution tends to deteriorate. Further, if the AA exceeds 4.0, the oxygen permeability will be lowered, and the resolution will be lowered for the reasons described above, which is not preferable.

The copolymer of AA and DAA is prepared by converting the aqueous solution of DAA and AA into 2,2'-azobis (2-amidinopropane) hydrochloride (hereinafter referred to as "V-50"), or A persulfate such as potassium persulfate, and a so-called redox catalyst using the same may be used as an initiator for polymerization, but the synthesis is not limited thereto. Further, the above DAA and the above AA are used as main monomer components, and in order to improve their developability, coatability, adhesiveness, etc.,
Small amounts of other monomers, such as hydrophobic monomers, sulfonic acid carboxylic acids, monomers having hydroxyl groups, N, N-
A ternary or higher copolymer obtained by copolymerizing dimethylacrylamide, N-vinylpyrrolidone and the like can also be preferably used.

The copolymerization of the above AA and the above DMAA is carried out in a molar ratio of monomers of 1 for DMAA and 0.05 for AA.
Copolymers in the range of -4.0 are preferred. This is the above A
When A is a copolymer of 0.05 or less, the oxygen permeability of the copolymer is too high, so that nitrene generated by exposure of an azide compound is easily quenched by oxygen. This is because the crosslinking reaction does not proceed, resulting in low sensitivity, which is not preferable. On the other hand, when AA exceeds 4.0, the viscosity of the copolymer becomes too high and the coatability tends to deteriorate. Further, generally speaking, the light passing through the shard mask spreads wider than the mask width of the shadow mask, but even if the spread light having low energy has low oxygen permeability in the film, it is easily photocured. This is because there is also a problem that the resulting resolution tends to deteriorate. If the above AA exceeds 4.0, the oxygen permeability will be lowered, and the resolution will be lowered due to the reasons described above, which is not preferable.

The above-mentioned copolymer of AA and DMAA is prepared by adding the aqueous solution of DMAA and AA to V-50,
Alternatively, a persulfate such as potassium persulfate and a so-called redox catalyst using the same may be used as an initiator for polymerization, but the present invention is not limited thereto.

Further, the above-mentioned DMAA and AA are used as main monomer components, and a small amount of another monomer such as a hydrophobic monomer, a sulfonic acid or a carboxyl group is used to improve the developability, water resistance, coating property, adhesiveness and the like. A ternary or higher copolymer obtained by copolymerizing an acid, a monomer having a hydroxyl group and the like, DAA, N-vinylpyrrolidone and the like can also be preferably used.

The preparation of cellulose derivatives having a quaternary nitrogen used in the composition of the present invention is described in USP262304.
2, JP-B-45-20318, JP-A-54-87
It can be obtained by the method described in JP-A No. 786, JP-A No. 54-87787, JP-A No. 1-138201. For example, the composition of the present invention can be obtained by reacting alkali cellulose with 2,3-epoxypropyltrialkylammonium chloride or the like, or reacting a cellulose substance with alkylene oxide and 2,3-epoxypropyltrialkylammonium chloride. The cellulose derivative having the quaternary nitrogen used can be obtained. In addition, Celquat L200 (Nation
al Starch Chemical) can also be used.

In the above cellulose derivative, the content of quaternary nitrogen is preferably 0.5 to 5% by weight. This is because if the amount is less than 0.5% by weight, the adhesiveness becomes insufficient.
This is because if the content is more than 10% by weight, the viscosity will be high and the coating property will be poor, both of which are not preferable.

Specific examples of the water-soluble azide compound used in the present invention are shown below in "Chemical formula 1", but the water-soluble azide compound usable in the present invention is not limited thereto.

[0034]

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[Chemical 4]

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[Chemical 6]

[Chemical 7]

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[Chemical 9]

In the above formulas "Chemical formula 1" to "Chemical formula 9", X
Is lithium, sodium, potassium, ammonium,
Monoalkyl ammonium, dialkyl ammonium,
It represents trialkylammonium or tetraalkylammonium.

Furthermore, JP-A-51-4956, JP-A-2-173007, JP-A-2-92905, JP-A-2-204750, JP-A-5-11442, JP-A-5-67433, and JP-A-5-67433. 5-113661, JP-A-6-32823, Japanese Patent Application No. 5-84375, Japanese Patent Application No.
Polymers containing a sulfonic acid group or a salt thereof and an azide group described in each publication such as -68354 can also be mentioned.

Among the above water-soluble azide compounds, those having two or more azide groups in one molecule have particularly good photocurability.

It is also possible to use a mixture of two or more of these compounds. These water-soluble azide compounds are preferably used in the range of 2 to 50% by weight based on the total weight of the copolymer of the water-soluble polymer and the cellulose derivative having a quaternary nitrogen. This is a water-soluble azide compound 2
If it is less than 50%, the sensitivity is not sufficient, while if it exceeds 50%, the physical properties of the coating film are deteriorated, and both are not preferable.

The water-soluble polymer and the water-soluble azide compound or the quaternary nitrogen-containing cellulose derivative and the water-soluble azide compound have good miscibility with each other, but have the water-soluble polymer and the quaternary nitrogen. In a photosensitive composition comprising a cellulose derivative and a water-soluble azide compound, when the content of the water-soluble azide is large, or when the content of the cellulose derivative having a quaternary nitrogen is large, the aqueous solution concentration of the photosensitive composition is When it is low, the photosensitive composition aqueous solution tends to become turbid. This is because a general water-soluble azide compound is anionic, and when it is added to a mixture of a water-soluble polymer and a cellulose derivative having a quaternary nitrogen, the water-soluble azide compound is a cationic polymer. It is considered that it exists only in the vicinity of the cellulose derivative having a quaternary nitrogen, which causes turbidity.

However, the addition of other salt here can avoid the turbidity of the photosensitive composition. The reason for this is not clear, but the addition of other salts causes the water-soluble azide compound not to exist only in the vicinity of the cellulose derivative having quaternary nitrogen, so that the water-soluble polymer and the cellulose derivative having quaternary nitrogen are uniformly distributed. It seems that it exists. As the other salt, either an inorganic salt or an organic salt may be used,
Since the inorganic salt has a large salting-out effect on the anionic azide compound which is a general water-soluble azide compound, the water-soluble azide compound used is limited in the case of the inorganic salt. On the other hand, organic salts are preferable to inorganic salts because they have less salting-out effect.

Specific examples of the organic salt used here are shown below, but the organic salt usable in the present invention is not limited thereto. Specific examples of other salts used in the present invention as organic salts include, for example, tetramethylammonium chloride, tetramethylammonium methylsulfate, tetramethylammonium p-toluenesulfonate, tetraethylammonium chloride, sodium p-toluenesulfonate. , Piperidine methanesulfonate, triethylamine methanesulfonate, sodium acetate and the like. Among these, tetraalkylammonium salts are preferable from the viewpoints of particularly good solubility and little salting-out effect.

Although the same effect as that of a salt can be obtained with an acid, addition of the acid lowers the pH of the photosensitive composition, which is not preferable. However, when the addition amount of the acid is small, an acid may be used instead of the salt depending on the application, and thus it may be appropriately selected as necessary.

The photosensitive composition of the present invention contains the above-mentioned water-soluble polymer, a quaternary nitrogen-containing cellulose derivative and a water-soluble azide compound, and various optional additives in a solvent containing water as a main component. It can be prepared by dissolving or dispersing.

As the solvent used at this time, water is generally used, and a solvent soluble in water at a ratio of 50% by weight or less, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, tetrahydrofuran, Dioxane, dimethylformamide, N-methylpyrrolidinone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and the like can be added.

If necessary, ethylene glycol, sorbitol, a surfactant or the like may be added to the photosensitive composition of the present invention to improve coating properties.

An antiseptic agent, a defoaming agent, and a pH adjusting agent may be added to the photosensitive composition of the present invention, if necessary.

If necessary, a hydrophobic polymer emulsion may be added to the photosensitive composition of the present invention in order to improve film strength, water resistance, adhesion to various substrates and the like.
Here, examples of the hydrophobic emulsion include polyvinyl acetate emulsion, polyacrylic acid ester emulsion, and urethane emulsion, but the present invention is not limited thereto.

Further, in order to prevent halation due to exposure or to obtain a colored image, a colorant such as a pigment or a dye may be added to the photosensitive composition of the present invention, if necessary.

In particular, the colored image obtained by dispersing the pigment in the photosensitive composition of the present invention can be applied to a color filter for liquid crystal display, a color proof for printing, a second original drawing and the like.

The pattern forming method using the photosensitive composition of the present invention will be described below.

(1) Process of Forming Coating Film of Photosensitive Composition on Substrate As the substrate, all substrates to which the photosensitive composition of the present invention can be adhered can be used. Specific examples of the substrate used in the present invention are shown below, but the substrate usable in the present invention is not limited to these. That is, specific examples of the substrate include, for example, soda glass, glass treated with SiO ₂ and ITO-coated glass; various plastic films such as polyester film, polyamide film, polyvinyl chloride film, polypropylene film; various metals. Examples include substrates, plastic plates and plastic films in which metals are laminated, plastics, metal meshes, silicon wafers, and the like.

Examples of the method for applying the photosensitive composition of the present invention include a spin coating method, a roll coating method, a curtain coating method, an applicator method and the like which have been generally used conventionally. After coating, a coating film is obtained by drying at a predetermined temperature according to a conventional method.

(2) Pattern exposure step As a light source for exposing the coating film of the above-mentioned photosensitive composition, there is used a light source having a wavelength which a water-soluble azide compound, such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp or a chemical lamp, is used. All common light sources that emit light can be used. As the exposure method, all general exposure methods such as reduction projection exposure method, contact exposure method and proximity exposure method can be used.

(3) Developing Step The pattern-exposed coating film of the photosensitive composition is formed with water, a mixed solvent of water and a water-soluble solvent, an acid, an alkali, an aqueous solution in which a surfactant, a buffer, or the like is dissolved. Can be developed. As the developing method, a general method such as spray developing, depping developing, or paddle developing can be used. When the method for forming the pattern of the present invention is applied to the inner surface of the face plate of the color cathode ray tube by the above method, the adhesiveness, the stability over time, the resolution and the like are good, and the productivity is good. After forming the pattern, graphite is applied and treated with a stripping solution to form a black matrix.
Since the pattern formed according to the present invention has a good releasability, a clean black matrix can be formed.

[0055]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 Polyvinylpyrrolidone (K-90 manufactured by ISP): 10.0 gr 4,4'-diazidostilbene-2,2'-sodium disulfonate (hereinafter referred to as "DAzST (Na)"): 1.0 gr 2 wt% aqueous solution of a cellulose derivative having quaternary nitrogen (Catinal HC-100; manufactured by Toho Kagaku Co., Ltd.): 50 gr Tetramethylammonium chloride 2 wt% aqueous solution: 55 gr Pure water: 484 gr First, as a weight ratio, [polyvinylpyrrolidone : DAz
ST (Na) = 100: 10] and [polyvinylpyrrolidone: cellulose derivative having quaternary nitrogen = 100:
10] is added to the photosensitive composition of the above formulation in an amount of 0.5 u
Filter with a membrane filter. Next, this filtered product was applied to the inner surface of the face plate of the color CRT by the so-called spin coating method, and dried at 50 ° C. for 1 minute to obtain a coating film of 0.65 μm. Next, hole diameter 135um
Distance between shadow mask and face plate of 1 cm, distance between shard mask and ultra high pressure mercury lamp 30 cm, illuminance of 350 nm on face plate surface 0.15 (mw / cm)
Under the exposure conditions of 2), the respective positions corresponding to "green", "blue", and "red" were exposed for 20 seconds. The relative humidity at the time of exposure was 45%. Subsequently, spray development was performed with water (nozzle: No. 0.3 manufactured by Spraying System Co., Ltd., water pressure: 2.0 (kg / cm 2), temperature: 40 ° C., distance 15 c).
m).

When the above-obtained pattern was observed with a microscope, there was no peeling of the pattern on all surfaces, and a pattern faithful to the shadow mask was obtained. A graphite dispersion (Hitasol Metallurgy Co., Ltd .: Hitasol 66S) was applied to the patterned face plate in an amount of 1.0 um, dried at 50 ° C. for 2 minutes, and then dipped in a 5% sulfuric acid solution at 40 ° C. for 30 seconds. Nozzle: No.2 made by Spraying System, water pressure:
Spraying was performed with water for 30 seconds under the conditions of 2.0 (kg / cm2), temperature: 40 ° C., and distance of 5 cm. As a result, the pattern dots and the graphite adhering to the pattern dots were peeled off together to obtain matrix holes. When the obtained matrix hole was observed with a microscope, it was a matrix hole faithful to the pattern.

When the above photosensitive composition was stored at 30 ° C. in the dark and visually inspected after 3 weeks, there was no change. Moreover, when the same evaluation as the above was performed, the same result was obtained.

Comparative Example 1 The same procedure as in Example 1 was repeated except that the polyvinylpyrrolidone-based photosensitive composition of Example 1 was omitted except that the cellulose derivative having quaternary nitrogen and the aqueous tetramethylammonium chloride solution were omitted. Then, the adhesiveness, sensitivity, and resolution were measured under the same evaluation conditions. As a result, even if the exposure time of 30, 60, and 90 seconds was given, all the patterns were peeled off during development, and the adhesiveness was poor.

Comparative Example 2 A silane coupling agent (KBM-603) was added to the photosensitive composition of Comparative Example 1 in an amount of 0.15.
The photosensitive composition containing gr was measured for adhesiveness, sensitivity and resolution under the same evaluation conditions as in Example 1. As a result, the same result as in Example 1 was obtained when the exposure time was 20 seconds. The above photosensitive composition was stored at 30 ° C. in the dark, and after three weeks, visual inspection revealed that a small amount of turbidity had occurred. When the same evaluation as above was carried out, a small amount of pattern loss was observed after development, and a slight decrease in adhesiveness was observed.

<Example 2> In a 1 liter reactor equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas introducing tube, D
MAA 20.5 gr, AA 14.84 gr (molar ratio DM
AA: AA = 1: 1), put 460gr of pure water, 60 ℃
Nitrogen gas was passed for 2 hours while maintaining the temperature to replace oxygen in the apparatus and in the monomer aqueous solution, and then V-5 was added to pure water 9 gr.
An aqueous solution obtained by adding 0.1 gr of 0 was added. While stirring the reaction solution, polymerization was carried out at the same temperature for 5 hours. The copolymer thus obtained had a residual monomer amount of 0.1% or less as a result of measurement by GPC (gel permeation chromatography). The viscosity of the obtained copolymer was 6100 cp (25 ° C).

A photosensitive composition having the following formulation was prepared. 7.12 wt% aqueous solution of the above copolymer: 140.4 gr DAzST (Na): 1.0 gr 2 wt% aqueous solution of cellulose derivative having quaternary nitrogen (Catinal HC-100; manufactured by Toho Chemical Co., Ltd.): 10 gr tetramethylammonium chloride 2 wt% aqueous solution: 3.5 gr Pure water: 364 gr First, as a weight ratio, [copolymer solid content: DAzST
(Na) = 100: 10] and [copolymer: cellulose derivative having quaternary nitrogen = 100: 1], and the photosensitive composition having the above formulation is filtered through a 0.5 um membrane filter. Next, this filtered product was applied to the inner surface of the face plate of the color CRT by the so-called spin coating method, and dried at 50 ° C. for 1 minute to obtain a coating film of 0.65 μm. Next, the distance between the shadow mask with a hole diameter of 135 um and the face plate is 1 cm, the distance between the shard mask and the ultra-high pressure mercury lamp is 30 cm, and the face plate surface is 350 cm.
Under the exposure condition of an illuminance of 0.15 (mw / cm 2) of nm, each of the positions corresponding to green, blue and red was exposed for 8 seconds. The relative humidity at the time of exposure was 45%. Subsequently, spray development was performed with water (nozzle: N manufactured by Spraying System Co., Ltd.).
o0.3, water pressure: 2.0 (kg / cm2), temperature: 40
C, distance 15 cm). When the obtained pattern was observed with a microscope, a pattern faithful to the shadow mask was obtained. A graphite dispersion (Hitasol Metallurgy Co., Ltd .: Hitasol 66S) was applied to the patterned face plate in an amount of 1.0 um, dried at 50 ° C. for 2 minutes, and then dipped in a 5% sulfuric acid solution at 40 ° C. for 30 seconds. Nozzle: No. 2 manufactured by Spraying System Co., Ltd., water pressure: 2.0 (kg / cm 2), temperature: 40 ° C., spraying with water for 30 seconds under conditions of a distance of 5 cm. As a result, the pattern dots and the graphite adhering to the pattern dots were exfoliated together to obtain matrix holes. When the obtained matrix hole was observed with a microscope, it was a matrix hole faithful to the pattern.

Comparative Example 3 DMAA-A of Example 2 above
A photosensitive composition obtained by omitting the cellulose derivative having a quaternary nitrogen and the tetramethylammonium chloride aqueous solution from the A-based photosensitive composition was operated in the same manner as in Example 2, and the adhesiveness, sensitivity and resolution were evaluated under the same evaluation conditions. Was measured. As a result, even if the exposure time of 30, 60, and 90 seconds was given, all the patterns were peeled off during development, and the adhesiveness was poor.

Example 3 A copolymer having a DAA: AA = 1: 2.0 molar ratio was synthesized under the same conditions as in Example 2 above, and the DMAA-AA copolymer in Example 2 was used instead. A photosensitive solution having exactly the same composition except that the above-prepared diacetone acrylamide-AA copolymer was used, and the sensitivity and resolution were measured under the same evaluation conditions. When the exposure time was 15 seconds, the same pattern as in Example 2 was obtained.

<Comparative Example 4> DAA-AA of the above Example 3
The photosensitive composition obtained by omitting the cellulose derivative having a quaternary nitrogen and the aqueous solution of tetramethylammonium chloride from the photosensitive composition was treated in the same manner as in Example 3, and the adhesiveness, sensitivity and resolution were evaluated under the same evaluation conditions. It was measured. As a result, even if the exposure time of 30, 60, and 90 seconds was given, all the patterns were peeled off during development, and the adhesiveness was poor.

[0066]

As described above, according to the present invention, since it has excellent adhesiveness, sensitivity and resolution, and stability over time,
A black matrix for color cathode ray tubes with good productivity and contrast can be manufactured.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideo Kikuchi 563 Yonegasaki, Funabashi City, Chiba Toyo Gosei Co., Ltd. Photosensitive Material Research Laboratory

Claims (11)

[Claims] 1. A photosensitive composition comprising a water-soluble polymer, a cellulose derivative having a quaternary nitrogen, and a water-soluble azide compound. 2. The photosensitive composition according to claim 1, wherein the weight ratio of the water-soluble polymer to the cellulose derivative having the quaternary nitrogen is such that the water-soluble polymer has a ratio of 1 to quaternary nitrogen. The photosensitive composition is characterized in that the cellulose derivative has a range of 0.001 to 0.2. 3. The photosensitive composition according to claim 1, wherein the content of the quaternary nitrogen in the cellulose derivative having the quaternary nitrogen is 0.5 to 5% by weight. A photosensitive composition to be used. 4. The photosensitive composition according to claim 1, 2 or 3, wherein the water-soluble azide compound is in the range of 2 to 50% by weight based on the total weight of the water-soluble polymer and the quaternary cellulose derivative. And a photosensitive composition. 5. The photosensitive composition according to claim 1, 2, 3 or 4, wherein the water-soluble polymer is polyvinylpyrrolidone having a K value of 30 or more. 6. The photosensitive composition according to claim 1, 2, 3, or 4, wherein the water-soluble polymer has a molar ratio of diacetone acrylamide and acrylamide as a monomer, and the diacetone acrylamide has a molar ratio of 1. On the other hand, a photosensitive composition characterized in that the acrylamide is a copolymer in the range of 1.5 to 4.0. 7. The photosensitive composition according to claim 1, 2, 3 or 4, wherein the water-soluble polymer has a molar ratio of N, N-dimethylacrylamide and acrylamide as a monomer. A photosensitive composition characterized in that it is a copolymer in which the acrylamide is in the range of 0.05 to 4.0 with respect to 1 of dimethylacrylamide. 8. The photosensitive composition according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the total weight of the water-soluble polymer, a cellulose derivative having a quaternary nitrogen and a water-soluble azide compound. To 0.1% salt
% To 20% by weight of the photosensitive composition. 9. The photosensitive composition according to claim 8, wherein the salt contained is a tetraalkylammonium salt. 10. The method according to claim 1, 2, 3, 4, 5, 6, 7,
8 or 9 to form a coating film by coating the photosensitive composition on a substrate, the step of exposing the coating film of the photosensitive composition to a desired pattern, and the coating of the photosensitive composition subjected to the pattern exposure And a step of developing the film with water or a water-based developing solution. 11. The pattern forming method according to claim 10, wherein the substrate on which the pattern is to be formed is an inner surface of a face plate of a color cathode ray tube.