JP2002323765A - Photosensitive composition, method for forming pattern by using the same and method for manufacturing cathode ray tube - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition having high sensitivity and excellent developing property and reciprocity law failure property as a water soluble photosensitive composition to be used for the manufacture of a black matrix type color cathode ray tube or the like. SOLUTION: The photosensitive composition consists of a water-soluble azide compound and a polymer compound prepared by copolymerizing at least one kind of amide between acrylamide and methacrylamide with diacetone acrylamide and vinyl imidazole.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive composition, a method of forming a pattern using the same, and a method of manufacturing a cathode ray tube.

[0002]

2. Description of the Related Art As an example of a conventional pattern forming method,
JP-A-48-90185, JP-A-50-3376
No. 4 describes a method for producing a black matrix of a color cathode-ray tube, and these publications describe a photosensitive composition used therein. This method uses a photosensitive composition having reciprocity failure characteristics, for example, a composition comprising a polymer compound such as an acrylamide-diacetone acrylamide copolymer and a bisazide-based cross-linking agent (photosensitive compound). This is a method of forming a pattern having a substantially smaller area.

[0003] This method will be described in detail. A black matrix type color cathode ray tube has a structure in which a panel has a phosphor pattern such as red, blue, and green phosphor dots or stripes on the inner surface thereof, and a gap between them is filled with a non-light-emitting light-absorbing substance such as carbon. . Hereinafter, a method of manufacturing a dot will be described for convenience of description. First, a coating film of the photosensitive composition having the reciprocity failure property is formed on the inner surface of the color cathode ray tube face plate, the positions where the phosphor dots are formed are exposed through a shadow mask, and the photosensitive composition is developed and developed. Form dots. Carbon is applied thereon, and the dots are removed together with the carbon thereon using a stripper. Thus, a black matrix hole is formed. Red, blue, and green phosphor dots are sequentially formed in this hole. Since the photosensitive composition having the reciprocity failure property is used, the area of the dot of the photosensitive composition, that is, the area of the phosphor dot is substantially smaller than the area irradiated with light through the shadow mask. Therefore, if a color cathode ray tube is completed using this shadow mass, the diameter of the electron beam irradiated through the hole of the shadow mask is larger than that of the fluorescent dot. Therefore,
The manufactured color CRT is bright and has excellent contrast.

[0004]

The prior art described above does not consider the use of this pattern forming method in the manufacture of large color cathode ray tubes. In the case of manufacturing a large color cathode ray tube, the illuminance on the exposed surface was reduced because the exposed surface was far from the light source, and it took a long time for exposure. Further, in the above-mentioned conventional technique, development took a long time.
If a composition having high sensitivity and capable of reducing the development time can be obtained, not only can the operation time be reduced, but also the consumption of hot water for development can be saved.

A first object of the present invention is to provide a photosensitive composition which has high sensitivity, can shorten the development time, and exhibits reciprocity failure characteristics. A second object of the present invention is to provide a pattern forming method using such a photosensitive composition. A third object of the present invention is to provide a method for manufacturing a cathode ray tube using such a photosensitive composition.

[0006]

Means for Solving the Problems In order to achieve the first object, the photosensitive composition of the present invention comprises at least one of acrylamide and methacrylamide,
It is composed of a polymer compound comprising diacetone acrylamide and vinylimidazole and a water-soluble azido compound.

In order to achieve the second object,
The pattern forming method of the present invention is a step of forming any one coating film of the photosensitive composition of the present invention having reciprocity failure characteristics on a surface on which a desired pattern is to be formed, The method includes a step of exposing a desired pattern under conditions where oxygen is present, and a step of forming a pattern by developing a coating film.

In order to achieve the third object,
The method for manufacturing a cathode ray tube according to the present invention includes the steps of:
A step of forming a coating film containing a photosensitive composition having reciprocity failure characteristics, a step of irradiating the coating film with radiation through a shadow mask, and a step of developing the coating film after irradiation with a developer And any one of the photosensitive compositions of the present invention is used as the photosensitive composition.

The above-mentioned polymer compound is a copolymer obtained by copolymerizing the above-mentioned monomers. Acrylamide or methacrylamide has a structure of the following formula 1 by polymerization. In the formula, R represents H or CH ₃ . Similarly, diacetone acrylamide and vinylimidazole have the following formulas 2 and 3, respectively.

[0010]

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[0011]

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[0012]

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The composition ratio of the monomer in the polymer compound is preferably in the range of 20 mol% to 100 mol% of diacetone acrylamide based on the amide, and
A range of 67 mol% is more preferred. The reason is that if the amount of diacetone acrylamide exceeds 67 mol% with respect to the amide, the solubility of the polymer compound in water becomes slightly poor, and if it exceeds 100 mol%, it becomes even worse. On the other hand, if the amount is less than 33 mol%, the coatability is slightly deteriorated, and if it is less than 20 mol%, the coatability is further deteriorated.

The vinylimidazole is preferably in the range of 0.01 mol% to 100 mol%, more preferably in the range of 1 mol% to 30 mol%, based on the amide.
The reason is that when the amount of vinylimidazole is 0.01 mol% or more based on the amide, the solubility of the polymer compound in water is improved, and when the amount is 1 mol% or more, the solubility of the polymer compound in water is further improved. Because. Also,
If the amount exceeds 30 mol%, the characteristics of the film slightly change. If the amount exceeds 100 mol%, the characteristics of the film further change.

The above-mentioned high molecular compound is used for the purpose of changing the solubility in water and improving the miscibility with other polymers added to the composition, and for the purpose of improving the miscibility with other polymers added to the composition.
Alternatively, an allyl monomer may be added. Examples of vinyl and / or allyl monomers include acryloylmorpholine, methacryloylmorpholine, N, N-dimethylacrylamide, N-ethylacrylamide, N-
Isopropylacrylamide, acrylamidepropanesulfonic acid, dimethylaminopropylacrylamide,
Acrylic acid and its salts, methacrylic acid and its salts, maleic acid and its salts, monoethyl maleate, hydroxylethyl acrylate, styrenesulfonic acid and its salts, vinylsulfonic acid and its salts, allylsulfonic acid and its salts, Examples include methacrylsulfonic acid and salts thereof, vinyl pyrrolidone, vinyl pyridine, allyl alcohol, methacryl alcohol, vinyl methyl ether, vinyl alcohol and the like. The compounds listed here are not always used as raw materials of the copolymer. For example, polyvinyl alcohol is obtained by polymerizing vinyl acetate as a raw material and hydrolyzing. If the structure in the copolymer is formally the same as when a certain monomer (eg, vinyl alcohol) is polymerized, the monomer is included in the water-soluble vinyl monomer. Is treated as.

The amount of the other vinyl and / or allyl monomer is preferably in the range of 5% (as a monomer unit) to 0.1% of the polymer compound. When the content is less than 5%, good reciprocity failure characteristics can be maintained.

These polymer compounds include 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2- (2-imidazolin-2-yl) propane) dihydrochloride and the like. Azo-based polymerization initiators, persulfates such as potassium persulfate and ammonium persulfate, and redox catalysts using these can be used as initiators for copolymerization.

The water-soluble azide compound includes 4,
4'-diazidostilbene-2, 2'-disulfonic acid disodium salt, 4,4'-diazidobenzalacetone-
2,2'-disulfonate disodium salt, etc.
No. 4,389,91 can be used. Further, a copolymer described in JP-A-1-302348, such as a maleic acid-4-vinylmonoazidobenzylideneacetophenone sodium sulfonate copolymer, can be used. In addition, Japanese Unexamined Patent Application Publication No.
Compounds described in JP-A-92905, JP-A-2-173007, JP-A-2-204750, JP-A-4-26849, JP-A-4-50205 and the like can be used. In addition, these compounds are
A mixture of more than one species can be used.

The proportion of the polymer compound and the water-soluble azide compound in the photosensitive composition of the present invention is preferably 1 to 50% by weight based on the polymer compound.
In particular, the range of 5 to 25% by weight is more preferable. The reason is that if the content is less than 5% by weight, the sensitivity of the photosensitive composition deteriorates,
This is because the sensitivity is further reduced when the amount is less than% by weight. Also, 2
If the content exceeds 5% by weight, the coating properties will be poor, and if it exceeds 50% by weight, the application will be even worse.

The photosensitive composition of the present invention may contain another water-soluble polymer compound compatible with the above composition. The reason for adding the water-soluble polymer compound is to improve the characteristics of the photosensitive composition as a paint, such as fluidity and coatability, and to improve the characteristics of the coating film. As such a water-soluble polymer compound, for example, methyl cellulose,
Cellulose such as hydroxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin,
Polyacrylamide, polymethacrylamide, acrylamide-diacetone acrylamide copolymer, methacrylamide-diacetone acrylamide copolymer, acrylamide-acryloylmorpholine copolymer, methacrylamide-acryloylmorpholine copolymer, and the like, but are not limited thereto. It does not do. Further, two or more of these water-soluble polymer compounds may be used simultaneously.

The photosensitive composition of the present invention is added with ethylene glycol, sorbitol or a surfactant for improving coating properties and coating properties, and vinyl tris (β- Coupling agents such as methoxyethoxy) silane can also be added. It is known that these substances can be added in order to improve the above-mentioned properties, and are disclosed in JP-A-48-90185 and JP-A-50-90185.
These matters are disclosed in, for example, JP-A-33764.

In the pattern forming method of the present invention, it is necessary to perform exposure under the condition that gaseous oxygen exists. Further, it is preferable that the exposure is performed in a range where the value of the Schwarzschild's constant p is 0 <p <0.76. The Schwarz-Baltz constant and reciprocity failure are described in the above-mentioned JP-A-48-48.
90185 and JP-A-50-33764.

[0023]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below in detail with reference to FIG. 1 by taking as an example a method of manufacturing a cathode ray tube for forming a black matrix pattern on a face panel. The photosensitive composition applied to the face panel includes at least a water-soluble polymer as a base resin and a photosensitive agent.

First, a black matrix of a phosphor screen is formed using the above photosensitive composition. The photosensitive composition is 1 to
A solution dissolved in water so as to have a thickness of about 5% by weight is coated on the inner surface of the face panel 1 of the color cathode ray tube to a thickness of 0.1 to
The photosensitive composition layer is exposed through a shadow mask 4 to a thickness of 1.0 μm and dried. Next, development is performed with water to remove unexposed portions, and a photocured pattern is formed on the inner surface of the face panel 1. Subsequently, a liquid containing a light-absorbing substance (carbon) is applied to the entire inner surface of the face panel 1 and dried. Next, the cured portion of the photosensitive composition and the light-absorbing substance on the cured portion of the photosensitive composition are peeled and removed by a lift-off method using a release agent to form a black matrix pattern. Further, a photosensitive paint containing each of red, blue, and green phosphors was sequentially applied, dried, solidified by light irradiation, and developed to form respective phosphor dots, thereby forming a phosphor screen 3. Hereinafter, the funnel 2, the neck 5, and the electron gun 6 are attached, and a color CRT is manufactured in the usual manner.

Hereinafter, the contents of the present invention will be described more specifically with reference to Examples and Comparative Examples.

(Example 1) 67.26 g of acrylamide, 68.14 g of diacetone acrylamide and 4.60 g of vinylimidazole were placed in a 2000 ml separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube, and a thermometer.
And 1860 g of water were taken and dissolved while stirring with nitrogen replacement. This was heated to 60 ° C., and 5 ml of an aqueous solution of 0.30 g of 2,2′-azobis (2- (2-imidazolin-2-yl) propane) dihydrochloride was added to initiate polymerization. In this state, the mixture was polymerized for 4 hours and cooled to obtain a copolymer. Almost all monomers of the reaction product thus obtained are polymerized. The viscosity of this 1.5% aqueous solution was 18.3 mPa · s, and the pH was 7.83.

As a cross-linking agent for the solid content of this aqueous solution, 10% by weight of 4,4'-diazidostilbene-2,2'-disulfonate disodium salt, 100% by weight of ethylene glycol, 0.1% of a silane coupling agent. 1% by weight was added to obtain a photosensitive composition aqueous solution. This aqueous solution of the photosensitive composition was spin-coated on the inner surface of a color cathode-ray tube to a thickness of 0.7 μm and dried to form a coating film. Ultraviolet exposure was performed using a shadow mask as a mask and an ultra-high pressure mercury lamp as a light source. At that time, the sensitivity was 3.8 mJ. Then 4
Using hot water at 0 ° C., spray development was performed at 2.0 kg / cm ² for 30 seconds to obtain well-shaped negative pattern dots. This photosensitive composition exhibited reciprocity failure characteristics.

Next, a carbon suspension was applied onto the dots, and a black matrix was formed by removing the dots and carbon on the dots with a stripping solution. Red, blue,
A photosensitive coating material containing each green phosphor was sequentially applied, dried, solidified by light irradiation, and developed to form each phosphor dot. Hereinafter, a color CRT was manufactured in the usual manner.

(Example 2) 60.05 g of acrylamide and diacetone acrylamide 7 were added to the reaction vessel of Example 1.
1.48 g, 8.47 g of vinylimidazole and 1860 g of ion-exchanged water were added and treated in the same manner as in Example 1.
The viscosity of a 1.5% aqueous solution of the obtained copolymer is 17.4 m
At Pa · s, the pH was 8.03. The same photo-crosslinking agent as in Example 1 was added, and the same treatment was performed thereafter. At that time, the sensitivity was 2.7 mJ. The development was completed completely in 25 seconds, and a well-shaped negative pattern dot was obtained. This photosensitive composition also exhibited reciprocity failure characteristics.

Next, in the same manner as in Example 1, a black matrix was formed, and further, red, blue, and green phosphor dots were formed. Hereinafter, a color CRT was manufactured in the usual manner.

Example 3 49.07 g of acrylamide and diacetone acrylamide 5 were added to the reaction vessel of Example 1.
8.43 g, vinylimidazole 32.50 g, and ion-exchanged water 1860 g were added, and the mixture was treated in the same manner as in Example 1. The viscosity of a 1.5% aqueous solution of the obtained copolymer is 13.
At 8 mPa · s, the pH was 8.43. The same photo-crosslinking agent as in Example 1 was added, and the same treatment was performed thereafter. The sensitivity at that time was 2.4 mJ. The development was completed completely in 22 seconds, and a good-shaped negative pattern dot was obtained.
This photosensitive composition also exhibited reciprocity failure characteristics.

Next, in the same manner as in Example 1, a black matrix was formed, and further, red, blue, and green phosphor dots were formed. Hereinafter, a color CRT was manufactured in the usual manner.

Example 4 51.62 g of acrylamide and diacetone acrylamide 8 were added to the reaction vessel of Example 1.
1.93 g, 6.45 g of vinylimidazole and 1860 g of ion-exchanged water were added and treated in the same manner as in Example 1.
The viscosity of a 1.5% aqueous solution of the obtained copolymer is 17.7 m.
At Pa · s, the pH was 8.11. The same photo-crosslinking agent as in Example 1 was added, and the same treatment was performed thereafter. At that time, the sensitivity was 2.9 mJ. Further, the development was completed completely in 30 seconds, and good-shaped negative pattern dots were obtained. This photosensitive composition also exhibited reciprocity failure characteristics.

Next, a black matrix was formed in the same manner as in Example 1, and further, red, blue, and green phosphor dots were formed. Hereinafter, a color CRT was manufactured in the usual manner.

Example 5 35.79 g of acrylamide and diacetone acrylamide 5 were added to the reaction vessel of Example 1.
6.82 g, vinyl imidazole 47.39 g and ion-exchanged water 1860 g were added, and the mixture was treated in the same manner as in Example 1. The viscosity of a 1.5% aqueous solution of the obtained copolymer is 12.
At 8 mPa · s, the pH was 8.46. The same photocrosslinking agent as in Example 1 was added, and the same treatment was performed. At that time, the sensitivity was 2.1 mJ. Further, the development was completed completely in 20 seconds, and a well-shaped negative pattern dot was obtained. This photosensitive composition also exhibited reciprocity failure characteristics.

Next, in the same manner as in Example 1, a black matrix was formed, and further, red, blue, and green phosphor dots were formed. Hereinafter, a color CRT was manufactured in the usual manner.

EXAMPLE 6 50.00 g of acrylamide and 5 ml of diacetone acrylamide were added to the reaction vessel of Example 1.
9.52 g, vinyl imidazole 15.00 g, acryloyl morpholine 15.48 g and ion-exchanged water 186
0 g was added and treated in the same manner as in Example 1. The viscosity of a 1.5% aqueous solution of the obtained copolymer was 13.6 mPa · s,
pH was 8.05. The same photo-crosslinking agent as in Example 1 was added, and the same treatment was performed. The sensitivity at that time is 2.1m
J. Further, the development was completed completely in 20 seconds, and a well-shaped negative pattern dot was obtained. This photosensitive composition also exhibited reciprocity failure characteristics.

Next, a black matrix was formed in the same manner as in Example 1, and further, red, blue, and green phosphor dots were formed. Hereinafter, a color CRT was manufactured in the usual manner.

Comparative Example 1 69.55 g of acrylamide, 70.45 g of diacetone acrylamide, and 1860 g of water were placed in a 2000 ml separable flask equipped with a stirrer, a cooling tube, a nitrogen inlet tube, and a thermometer, and stirred while replacing with nitrogen. And dissolved. This was heated to 58 ° C., and thereto was added 5 ml of an aqueous solution of 0.20 g of 2,2′-azobis (2- (2-imidazolin-2-yl) propane) dihydrochloride to initiate polymerization. In this state, polymerization was carried out for 4 hours, followed by cooling to obtain a 7% by weight aqueous solution. Almost all monomers of the reaction product thus obtained are polymerized. This was diluted to obtain a 1.5% by weight aqueous solution of the copolymer. The viscosity of this aqueous solution is 19.7 mPa · s, and the pH is 5.1.
It was 3.

Thereafter, a photosensitive composition was prepared in the same manner as in Example 1, and subsequently the same operation was carried out to produce a color CRT in a usual manner. The sensitivity at this time is 4.0m
J, and required 40 seconds for development.

[0041]

As described above, the photosensitive composition of the present invention has high sensitivity and excellent developing characteristics, and exhibits reciprocity failure characteristics. Therefore, a good pattern can be formed using this photosensitive composition. In addition, for example, a large black matrix type color CRT can be efficiently manufactured. Further, a black matrix with good contrast can be manufactured even when used for manufacturing a high-definition black matrix type color CRT.

[Brief description of the drawings]

FIG. 1 is a sectional view showing the structure of a cathode ray tube according to the present invention.

[Description of Signs] 1 ... face panel, 2 ... funnel, 3 ... phosphor screen, 4
... shadow mask, 5 ... neck, 6 ... electron gun.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01J 9/227 H01J 9/227 D (72) Inventor Emiko Yamada 3300 Hayano, Mobara-shi, Chiba Hitachi, Ltd. F term in display group (reference) 2H025 AA01 AA04 AB17 AC01 AD01 BA06 BC19 BC20 BC23 BC24 CB15 FA03 FA17 4J002 BG131 BJ001 EQ036 GP03 GQ00 5C028 JJ01

Claims (5)

[Claims] 1. A photosensitive composition comprising a polymer compound comprising at least one amide of acrylamide and methacrylamide, diacetone acrylamide and vinylimidazole, and a water-soluble azido compound. 2. The composition ratio of the monomer of the polymer compound is as follows:
The diacetone acrylamide is in a range of 20 mol% to 100 mol% with respect to the amide, and the vinylimidazole is in a range of 0.01 mol% to 100 mol% with respect to the amide. Claim 1
The photosensitive composition as described in the above. 3. The polymer compound according to claim 1, wherein
3. The photosensitive composition according to claim 1, comprising at least one monomer selected from a vinyl monomer and an allyl monomer. 4. A step of forming a coating film of the photosensitive composition having reciprocity failure characteristics according to any one of claims 1 to 3 on a surface on which a desired pattern is to be formed. A step of exposing a desired pattern under conditions where oxygen is present, and a step of developing the coating film to form a pattern. 5. A step of forming a coating film containing a photosensitive composition having a reciprocity failure property on a face panel, a step of irradiating the coating film with radiation through a shadow mask, and a step of developing the coating film. Wherein the photosensitive composition comprises a step of developing with a liquid.
A method for producing a cathode ray tube, comprising the photosensitive composition according to any one of the above.