JPH11133596A - Photopolymerizable composition, pattern forming method using the same and manufacture of cathode ray tube - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photopolymerizable composition containing an unsaturated ethylene compound coatable with a water solvent and superior in photohardenability by incorporating a unsaturated ethylene compound. SOLUTION: This photopolymerizable composition contains the unsaturated compound represented by the formula and this composition has superior water solubility. The photopolymerizable composition comprises this unsaturated ethylene compound and at least a water-soluble polymer and a photopolymerization initiator, and when needed, a surfactant and the like. The water-soluble polymer is embodied by mehyl cellulose and polyvinylalcohol and the like. It is preferred that the proportion of each component is 100 pts.wt. of the water-soluble polymer and 30-200 pts.wt. of the unsaturated ethylene compound and 0.05-30 pts.wt. of the photopolymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble photopolymerizable composition and a method of forming a pattern using the same. The present invention relates to a photopolymerizable composition that enables development and a pattern forming method using the same.

[0002]

2. Description of the Related Art Photopolymerizable compositions are widely used for forming various patterns, for example, for letterpress, coating, and photoresist. Such a photopolymerizable composition,
Generally, it is composed of a binder polymer, an unsaturated ethylene compound (polymerizable oligomer or monomer), a radiation-sensitive compound (polymerization initiator by exposure), and other additives such as a polymerization inhibitor and a surfactant. When radiation is applied to such a composition, the radiation is absorbed by the radiation-sensitive compound to generate active radicals and cations. These active species cause a polymerization reaction of oligomers and monomers,
Useful cured products such as, for example, resists are obtained.

[0003] In recent years, interest in safety and economy related to environmental problems has been increasing, and water-based materials have attracted attention. In particular, a system using no organic solvent is desirable. As a water-soluble unsaturated ethylene compound, polyethylene glycol diacrylate (methacrylate) which is an alkyl acrylate (methacrylate) is known. As for the water-soluble photopolymerization initiator, sodium 4- [2- (4-morpholino) benzoyl-2-dimethylamino] butylsulfonate described in Japanese Patent Application No. 8-349264 is soluble in water and radical-generating efficiency. Both are excellent.

[0004] The photopolymerizable composition is used for forming various patterns as described above. For example, manufacturing of printed circuit boards by lithography technology (forming a resist mask on copper foil on an insulating substrate to form wiring conductor patterns) and manufacturing of a cathode ray tube faceplate (forming phosphor patterns and black matrix patterns) It is.

[0005] As a typical example of pattern formation, an example of manufacturing a cathode ray tube will be described. The cathode ray tube has a structure as shown in FIG. A panel (face plate) 1, a funnel 2 joined to the panel 1, a fluorescent screen 3 formed inside the panel 1, and a shadow mask 4 having an electron beam passage hole formed thereon are mounted. An electron gun 6 is provided inside the neck 5 of the funnel 2.

Conventionally, the fluorescent screen 3 of the cathode ray tube has been formed by photolithography using a slurry containing at least a resist made of polyvinyl alcohol and dichromate and a phosphor. The phosphor slurry is applied to the panel 1 of the cathode ray tube on which a black matrix is formed in advance, dried by heating, and then exposed through a mask using an ultra-high pressure mercury lamp. Subsequently, when spray development is performed with pure water, a phosphor pattern is formed. By sintering this, the phosphor screen 3 is formed.

[0007]

The above prior art has the following problems.

In recent years, the size of cathode ray tubes has been remarkably increased, and in the manufacture of large tubes, when exposing to phosphor slurry,
The distance between the face plate and the exposure light source is inevitably increased. Since the exposure intensity decreases in inverse proportion to the square of the distance, the exposure to a large tube requires a longer exposure time, which causes a problem that the production efficiency is reduced, and the demand for a highly sensitive phosphor slurry is increasing. I have.

As a conventional method of increasing the sensitivity of a phosphor slurry, for example, a method of adding an aromatic diazonium salt (Japanese Patent Laid-Open No. 57-9036) is known. However, in this method, there is a fatal problem that the aromatic diazonium salt has poor thermal stability, and a practical increase in sensitivity has not been achieved.

[0010] Further, the conventional photopolymerizable composition (resist composition) contains chromium which is harmful to living organisms, and thus has a problem in safety measures. Examples of the chromium-free resist include a photopolymerization resist previously proposed by the present inventors (Japanese Patent Application No. 8-5421).
No.). As a water-soluble photopolymerization initiator, a radiation-sensitive compound represented by the chemical formula (2) proposed by the present inventors (Japanese Patent Application No. 8-349264) is also suitable. However, in this method, tetramethylolmethane triacrylate, which is an unsaturated ethylene compound excellent in photocurability, is not water-soluble, so that water cannot be used at the time of coating.
On the other hand, polyethylene glycol dimethacrylate, which is a water-soluble unsaturated ethylene compound, has excellent solubility in water, but the photopolymerizable composition using the same has low sensitivity and poor curing properties. .

[0011]

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An object of the present invention is to solve the above-mentioned conventional problems, and a first object is to provide a photopolymerizable composition containing an unsaturated ethylene compound which can be coated with an aqueous solvent and has excellent photocurability. The second object is to provide a method for curing the photopolymerizable composition,
A third object is a pattern forming method using the photopolymerizable composition, and a fourth object is to use the water-soluble photopolymerizable composition containing no harmful chromium to form a phosphor layer or the like. An object of the present invention is to provide a method of manufacturing a cathode ray tube for forming a pattern of a black matrix on a face plate.

[0013]

The first object of the present invention is to provide an unsaturated ethylene compound represented by the following chemical formula (1).

[0014]

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This is achieved by a photopolymerizable composition comprising:

Since the unsaturated ethylene compound represented by the chemical formula (1) has excellent water solubility, a photopolymerizable composition that can be coated with an aqueous solvent can be obtained by using the compound. The photopolymerizable composition generally contains at least a water-soluble polymer and a photopolymerization initiator together with an unsaturated ethylene compound, and further contains a surfactant or the like as necessary.

Examples of uses of such a photopolymerizable composition include printing inks, color filters for displays, stereolithography, photoresists, coatings of optical fibers or metals, paints, adhesives and the like.

As the water-soluble polymer, those used in conventional cathode ray tube manufacturing can be used. Examples thereof include celluloses such as methylcellulose and hydroxymethylcellulose, homopolymers such as polyvinyl alcohol, polyacryloylmorpholine, polyacrylamide, polydimethylacrylamide, and polyvinylpyrrolidone, and acrylamide-diacetoneacrylamide copolymer.

The second object includes a step of applying the photopolymerizable composition on a desired substrate to form a coating film, and a step of irradiating the coating film with radiation containing light to cure the coating film. This can be achieved by the method for curing the photopolymerizable composition described above. The radiation is an ultraviolet ray, a visible ray, an electron beam, an ion beam, an X-ray, or the like, and can be appropriately selected depending on the application.

A third object is to apply a coating solution containing the photopolymerizable composition to a substrate surface to form a coating film, and to irradiate the coating film with radiation through a desired mask to expose the coating film. And a step of developing the exposed coating film with a developing solution.

As an object of pattern formation, it is preferable to manufacture various electronic parts by lithography technology. For example, when used in the manufacture of semiconductor devices, thin-film magnetic heads, printed circuit boards, cathode ray tubes for image display, etc., both the coating process of the photopolymerizable composition and the development process after exposure are performed without using an organic solvent and using an aqueous solution. Processing is possible, which is preferable from the viewpoint of safety related to environmental problems and also from the viewpoint of economy.

A fourth object is a specific application of the third object, wherein a coating solution obtained by dispersing a phosphor powder in the photopolymerizable composition is applied on a face panel. A method for producing a cathode ray tube, comprising the steps of: applying a fluorescent film to the coating film, irradiating the coating film with radiation through a shadow mask and exposing the coating film, and developing the exposed coating film with a developer. Can be achieved by:

If instead of dispersing the phosphor powder in the photopolymerizable composition, a powder made of a light absorbing material such as carbon powder is dispersed, a black matrix pattern is formed on the face plate (panel) in the same manufacturing process. Can be formed.

In such a method for producing a cathode ray tube, a harmful heavy metal (chromium), which has been a problem of the conventional photocurable composition, is not contained, and an organic solvent is not used in both the coating step and the developing step. It has an excellent effect that it can be treated with an aqueous material.

[0025]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be specifically described below by taking as an example a method of manufacturing a cathode ray tube for forming a pattern of a phosphor layer on a face panel.

The photopolymerizable composition applied to the face panel includes a water-soluble polymer, a radiation-sensitive compound (photopolymerization initiator),
It comprises an unsaturated ethylene compound represented by the chemical formula (1) and a phosphor.

The water-soluble polymer used here includes:
Those used in the production of conventional cathode ray tubes can be used. Examples thereof include celluloses such as methylcellulose and hydroxymethylcellulose, homopolymers such as polyvinyl alcohol, polyacryloylmorpholine, polyacrylamide, polydimethylacrylamide, and polyvinylpyrrolidone, and acrylamide-diacetoneacrylamide copolymer, but are not limited thereto. is not. One or more of these water-soluble polymers can be used in combination. The molecular weight of these water-soluble polymers ranges from 10,000 to 2,000,000.

As the radiation-sensitive compound (photopolymerization initiator) used here, a radiation-sensitive compound represented by the chemical formula (2) is suitable. As a typical example of the compound represented by the chemical formula (2), for example, R1 = morpholino group, R
Sodium 4- [2- (4-morpholino) benzoyl-2-dimethylamino] butylbenzenesulfonate consisting of 2 = ethyl group, R3 = dimethylamino group and R4 = sodium (chemical formula (3)), or R4 = potassium Done 4
-Potassium [2- (4-morpholino) benzoyl-2-dimethylamino] butylbenzenesulfonate (chemical formula
(4)).

[0029]

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[0030]

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The phosphor used here includes:
What has been used for the conventional fluorescent screen formation can be used.

The mixing ratio of each component in the present invention is such that the unsaturated ethylene compound 30
The range is preferably from 200 to 200 parts by weight and from 0.05 to 30 parts by weight of the photopolymerization initiator. The mixing ratio of the phosphor is 10
The range of 10 to 1,000 parts by weight relative to 0 parts by weight is preferred.

The photopolymerizable composition of the present invention may further contain, if necessary, a thermal polymerization inhibitor such as 4-methoxyphenol, hydroquinone, or catechol. It is also possible to add and use a surfactant.

In the method for manufacturing a cathode ray tube according to the present invention, the phosphor screen is formed by photolithography. Aqueous solution (slurry) of the above photopolymerizable composition in which phosphor powder is dispersed on a face panel on which a black matrix has been formed
Is applied. Subsequently, after exposing a predetermined position on the coating film surface by using an ultra-high pressure mercury lamp through a shadow mask, developing by a pure water spray, a phosphor pattern is obtained. By firing this, a desired phosphor screen can be obtained. Then, face plate baking is performed, the face plate portion and the funnel portion are combined and frit baked, and a cathode ray tube is manufactured through a process of mounting an electron gun. In the case of a color cathode ray tube, a slurry containing phosphors of three colors R, G, and B is prepared and applied, and the same type of pattern forming process is repeated three times to form a phosphor layer pattern of three colors. I do.

Example 1 Sodium 4- [2- (4-morpholino) benzoyl-2-dimethylamino] butylbenzenesulfonate (100 mg of the above formula (3))
2.0 g of polyvinylpyrrolidone and 1.5 g of the unsaturated ethylene compound represented by the chemical formula (1) were dissolved in 25 g of water. This polymer solution is spin-coated on a glass plate,
Heating at 2 ° C. for 2 minutes gave a film having a thickness of 2000 nm. This film was irradiated with light from a high-pressure mercury lamp through a step tablet (Kodak No. 2). After light irradiation, water development was performed for 40 seconds. The sensitivity of this composition was ² mJ / cm ² .

Therefore, the photopolymerizable composition of the present invention is
It was found that both coating and development could be carried out with an aqueous solvent, and that it had excellent photosensitivity.

Example 2 100 mg of potassium 4- [2- (4-morpholino) benzoyl-2-dimethylamino] butylbenzenesulfonate (chemical formula (4)), 2.0 g of polyvinylpyrrolidone, chemical formula (1) Was dissolved in 25 g of water. This polymer solution is spin-coated on a glass plate,
For 2 minutes to obtain a film having a thickness of 2000 nm. The film was irradiated with light from a high-pressure mercury lamp through a step tablet (Kodak No. 2). After light irradiation, water development was performed for 40 seconds. The sensitivity of this composition was ² mJ / cm ² .

Example 3 100 mg of sodium 4- [2- (4-morpholino) benzoyl-2-dimethylamino] butylbenzenesulfonate (the above chemical formula (3))
2.0 g of an acrylamide-diacetone acrylamide copolymer and 1.5 g of an unsaturated ethylene compound represented by the above formula (1) were dissolved in 25 g of water. The polymer solution was spin-coated on a glass plate and heated at 80 ° C. for 2 minutes to obtain a film having a thickness of 2000 nm. The film was irradiated with light from a high-pressure mercury lamp through a step tablet (Kodak No. 2).
After light irradiation, water development was performed for 40 seconds. The sensitivity of this composition was ² mJ / cm ² .

Example 4 100 mg of sodium 4- [2- (4-morpholino) benzoyl-2-dimethylamino] butylbenzenesulfonate (the above-mentioned chemical formula (3))
2.0 g of polyvinyl alcohol and 1.5 g of the unsaturated ethylene compound represented by the chemical formula (1) were dissolved in 25 g of water. This polymer solution is spin-coated on a glass plate,
Heating at 2 ° C. for 2 minutes gave a film having a thickness of 2000 nm. This film was irradiated with light from a high-pressure mercury lamp through a step tablet (Kodak No. 2). After light irradiation, water development was performed for 40 seconds. The sensitivity of this composition was 4 mJ / cm ² .

Comparative Example 1 100 mg of sodium 4- [2- (4-morpholino) benzoyl-2-dimethylamino] butylbenzenesulfonate, 2.0 g of polyvinylpyrrolidone, 1.5 g of polyethylene glycol # 1000 dimethacrylate and 25 g of water Was dissolved. The polymer solution was spin-coated on a glass plate and heated at 80 ° C. for 2 minutes to obtain a film having a thickness of 2 mm. The film was irradiated with light from a high-pressure mercury lamp through a step tablet (Kodak No. 2).
After light irradiation, water development was performed for 40 seconds. The sensitivity of this composition was 50 mJ / cm ² .

The composition of this comparative example was significantly inferior in light sensitivity as compared with the compositions of the present invention shown in Examples 1 to 3.

Example 5 100 parts by weight of polyvinylpyrrolidone having an average molecular weight of 700,000, 100 parts by weight of an unsaturated ethylene compound represented by the chemical formula (1), 4- [2- (4-morpholino) benzoyl-2-dimethyl Amino] sodium butylbenzenesulfonate 5 parts by weight, ZnS: Ag,
430 parts by weight of blue phosphor powder composed of Cl and 800 parts by weight of water were mixed to obtain a photopolymerizable composition (phosphor slurry). As shown in FIG. 1, this was applied to the inside of the face panel 1 of a cathode ray tube on which a black matrix had been formed in advance, and dried by heating.

Subsequently, light of 15 mJ / cm ² was irradiated through a shadow mask 4 using an ultra-high pressure mercury lamp and spray-developed with pure water for 1 minute to obtain a phosphor pattern. Hereinafter, following the sintering of the phosphor layer, the panel and the funnel portion were frit-baked in a usual manner, and a cathode ray tube was manufactured through a process of mounting an electron gun. Was obtained.
For the red and green phosphors, it was possible to produce cathode ray tubes in the same manner.

Comparative Example 2 A phosphor slurry having a composition conventionally used in the manufacture of a cathode ray tube, that is, an average molecular weight of 1
A cathode ray tube having a black matrix formed of a phosphor slurry composed of 100,000 parts by weight of 100,000 polyvinyl alcohol, 7 parts by weight of sodium dichromate, 430 parts by weight of a phosphor powder composed of (Zn, Cd) S: Ag, and 800 parts of water And dried by heating. Subsequently, exposure was performed using an ultra-high pressure mercury lamp through a mask, but an exposure amount of 100 mJ / cm ² was required to obtain a pattern of the phosphor.

[0045]

The photopolymerizable composition of the present invention can be applied and developed with an aqueous solvent, and has high sensitivity. Further, by using the same, a cathode ray tube can be manufactured with high efficiency without using harmful chromium.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a structure of a cathode ray tube.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Panel, 2 ... Funnel, 3 ... Phosphor screen, 4 ... Shadow mask, 5 ... Neck, 6 ... Electron gun.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03F 7/028 G03F 7/028 H01J 9/227 H01J 9/227 C (72) Inventor Morishita ▲ First ▼ 3300 Hayano, Mobara-shi, Chiba Address: Electronic Device Division, Hitachi, Ltd.

Claims (9)

[Claims] 1. A photopolymerizable composition containing an unsaturated ethylene compound represented by the chemical formula (1). Embedded image 2. The photopolymerizable composition according to claim 1, comprising at least a water-soluble polymer and a water-soluble photopolymerization initiator together with the unsaturated ethylene compound. 3. A photopolymerizable composition, wherein the water-soluble photopolymerization initiator according to claim 2 is represented by the chemical formula (2). Embedded image (Wherein R1 is a hydrogen atom, an amino group, a methylamino group,
A dimethylamino group, a diethylamino group, a diarylamino group, a pyrrolidino group, a piperidino group, a morpholino group, a hydroxyl group, a halogen atom, a methylthio group or a methoxy group. R2 represents a substituted or unsubstituted methyl, ethyl, aryl, normal propyl, isopropyl, butyl, phenyl or 1-propenyl.
R3 is an amino group, a methylamino group, a dimethylamino group,
It represents any of a diethylamino group, a diarylamino group, a pyrrolidino group, a piperidino group, and a morpholino group. R4 represents any of a hydrogen atom and an alkali metal atom such as sodium and potassium. ) 4. The water-soluble polymer according to claim 2, wherein the water-soluble polymer is methylcellulose, hydroxymethylcellulose, polyvinylpyrrolidone, polyvinylalcohol, polyacrylamide, polydimethylacrylamide, a copolymer of acrylamide and diacetoneacrylamide, polyethylene glycol and polyacryloylmorpholine. 3. The photopolymerizable composition according to claim 2, wherein the composition is at least one polymer selected from the group consisting of: 5. A method for curing a photopolymerizable composition, comprising the step of irradiating a radiation onto a substrate surface coated with the photopolymerizable composition to photocure the photopolymerizable composition. A method for curing a photopolymerizable composition comprising a composition comprising the photopolymerizable composition according to claim 1. 6. A step of applying a coating solution containing a photopolymerizable composition to a substrate surface to form a coating film, irradiating the coating film with radiation through a desired mask, and exposing the coating film; A step of developing the coating film with a developer in the pattern forming method, wherein the photopolymerizable composition comprises the photopolymerizable composition according to any one of claims 1 to 4. Method. 7. The pattern forming method according to claim 6, wherein both the coating solution containing the photopolymerizable composition and the developing solution are composed of an aqueous solution. 8. A step of applying a coating solution in which a phosphor powder is dispersed in a photopolymerizable composition to a face panel to form a fluorescent coating, and irradiating the coating with radiation through a shadow mask to expose the coating. And a step of developing the exposed coating film with a developing solution, wherein the photopolymerizable composition is a photopolymerizable composition according to claim 1. A method for manufacturing a cathode ray tube made of a product. 9. The method for manufacturing a cathode ray tube according to claim 8, wherein both the coating solution and the developing solution are composed of an aqueous solution.