JP2003076011A - Photosensitive composition and pattern forming method and method for producing cathode-ray tube using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition having excellent removability and reciprocity law failure as a water-soluble photosensitive composition used in the production of a black matrix type color cathode-ray tube. SOLUTION: A high molecular compound having a structural unit of vinylcaprolactam and a photosensitive composition containing the compound are used.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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 producing a color picture tube phosphor surface.
The present invention relates to a method for manufacturing a cathode ray tube using the same.

[0002]

2. Description of the Related Art As an example of a conventional pattern forming method, JP-A-48-90185 and JP-A-50-33764 are known.
The publication describes a method for producing a black matrix of a color cathode ray tube and a photosensitive composition used therefor. The pattern forming method described in this conventional example comprises a photosensitive composition having reciprocity failure characteristics, for example, a polymer compound such as acrylamide-diacetone acrylamide copolymer and a bisazide-based crosslinking agent (photosensitive composition). It is a method of using the composition to form a pattern having a substantially smaller area than the light irradiation area.

The above method will be described in detail. The black matrix type color cathode ray tube has a phosphor pattern such as red, blue and green phosphor dots or stripes on the inner surface of the panel, and has a structure in which voids between them are filled with a non-emissive light absorbing substance such as carbon. . Hereinafter, for convenience of description, a method of manufacturing a dot will be described.

First, a coating film of the photosensitive composition having the reciprocity law failure property is formed on the inner surface of the color cathode ray tube face plate, and the positions where the phosphor dots are formed are exposed through a shadow mask and developed to develop photosensitivity. Form dots of the composition. When carbon is applied on this and the dots are removed together with the carbon on the dot with a stripping solution, holes of black matrix are formed. Red, blue,
Form green phosphor dots.

Since a material having a reciprocity law failure characteristic is used for the coating film of the photosensitive composition, the area of the dots of the photosensitive composition, that is, the area of the phosphor dots is the shadow mask. Substantially smaller than the area illuminated by light. Therefore, if a color cathode ray tube is completed by 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.

[0006]

In the prior art described above, when the photosensitive compositions disclosed in JP-A-48-90185 and JP-A-50-33764 are used, the resist is insufficiently peeled off and the fluorescent surface is uniform. There was a problem that it was not formed.
Further, in order to solve these problems, there is a problem that the temperature for peeling and the time required for peeling take a long time. If a composition capable of stripping at a low temperature for a short time is obtained, not only the working time can be shortened but also hot water for stripping can be saved.

An object of the present invention is to provide a light-sensitive composition and a pattern forming method using the same, in which the above problems are improved. Another object of the present invention is to provide a photosensitive composition exhibiting reciprocity law failure characteristics and excellent photosensitive characteristics, and a pattern forming method using the same.

[0008]

In order to achieve the above object, the present invention provides a photosensitive composition comprising a polymer compound having a structure of Chemical Formula 1 and a photosensitive compound. The polymer compound of the present invention is obtained by radical polymerization of one or both of vinylcaprolactam (Chemical formula 2) and acrylamide (Chemical formula 3) or diacetone acrylamide (Chemical formula 4) and vinylpyrrolidone (Chemical formula 5). Furthermore, the photosensitive composition of the present invention is characterized by comprising a polymer compound and a water-soluble azide compound.

[0009]

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6] The polymer compound of the present invention is a copolymer. In addition to the above monomer units, other vinyl or allyl monomers may be added for the purpose of changing the solubility in water and improving the miscibility with other polymer additives.

As the vinyl or allyl monomer, acryloylmorpholine, methacryloylmorpholine,
N, N-dimethylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, acrylamidopropanesulfonic acid, dimethylaminopropylacrylamide, acrylic acid and its salts, methacrylic acid and its salts, maleic acid and its salts, maleic acid monoethyl ester , Hydroxylethyl acrylate, styrene sulfonic acid and its salts, vinyl sulfonic acid and its salts, allyl sulfonic acid and its salts, methacryl sulfonic acid and its salts, vinyl pyridine, allyl alcohol, methacrylic alcohol, vinyl methyl ether,
Vinyl alcohol etc.

The compounds listed here are not always used as the raw material of the copolymer. For example, polyvinyl alcohol is obtained by polymerizing vinyl acetate as a raw material and hydrolyzing it. In this way, if the structure in the copolymer is the same as when formally polymerizing a certain monomer (for example, vinyl alcohol), that monomer is included in the water-soluble vinyl monomer. Can be treated as

The amount of the other vinyl and / or allyl monomer is 20% (as a monomer unit) of the polymer compound.
To 0.1% is preferable. This is because if it is less than 20%, good reciprocity law failure is maintained.

These polymer compounds are 2,2'-azobis (2-amidinopropane) dihydrochloride and 2,2'-azobis (2- (2-imidazolin-2-yl) propane).
It can be synthesized by copolymerizing an azo polymerization initiator such as a dihydrochloride or potassium persulfate, a persulfate such as ammonium persulfate or a redox catalyst using these as an initiator.

In the case of a copolymer of vinylcaprolactam and acrylamide, the composition ratio of the monomers in the above copolymer is preferably in the range of 50 to 500 mol% of acrylamide to vinylcaprolactam, and 100 to 3%.
The range of 00 mol% is more preferable. The reason is that acrylamide is 300 mol% relative to vinylcaprolactam.
If it exceeds, the coating property will be deteriorated. Also, 100
This is because if it is less than 50 mol%, the solubility of the polymer compound in water will be poor, and if it is less than 50 mol%, the solubility will be further deteriorated.

In the case of a copolymer of vinylcaprolactam and vinylpyrrolidone, it is preferable that vinylpyrrolidone is 50 mol% or more with respect to vinylcaprolactam.
It is more preferably 100 mol% or more. The reason is 100
This is because if it is less than 50 mol%, the solubility of the polymer compound in water will be poor, and if it is less than 50 mol%, the solubility will be further deteriorated.

In the case of a copolymer of vinylcaprolactam, acrylamide and diacetone acrylamide, 50 to 500 acrylamide is contained for vinylcaprolactam.
The range of mol% is preferable, and the range of 100 to 400 mol% is more preferable. The reason is that if acrylamide exceeds 400 mol% with respect to vinylcaprolactam, the coating properties will be poor. Further, if it is less than 100 mol%, the solubility of the polymer compound in water is deteriorated, and if it is less than 50 mol%, the solubility is further deteriorated.

The amount of diacetone acrylamide relative to vinylcaprolactam is preferably 20 to 200 mol%, more preferably 50 to 150 mol%.
The reason is that when the amount of diacetone acrylamide exceeds 150 mol% with respect to vinyl caprolactam, the resist releasability deteriorates, and the amount exceeds 200 mol% and further deteriorates. Further, when the amount of diacetone acrylamide is less than 50 mol% with respect to vinylcaprolactam, a large amount of silane coupling agent is used to adhere the resist.

In the case of a copolymer of vinylcaprolactam, acrylamide and vinylpyrrolidone, acrylamide is preferably in the range of 50 to 700 mol%, more preferably 100 to 400 mol% with respect to vinylcaprolactam. The reason is that if acrylamide exceeds 700 mol% with respect to vinylcaprolactam, the coating properties will be poor. Further, if it is less than 100 mol%, the solubility of the polymer compound in water is deteriorated, and if it is less than 50 mol%, the solubility is further deteriorated.

The content of vinylpyrrolidone with respect to vinylcaprolactam is preferably 20 to 500 mol%, more preferably 50 to 300 mol%. The reason is that when the amount of vinylpyrrolidone exceeds 300 mol% with respect to vinylcaprolactam, the releasability of the resist is deteriorated, and more than 500 mol% is further deteriorated.

A water-soluble azide compound can be used as the photosensitive compound. Examples of the water-soluble azide compound include 4,4′-diazidostilbene-2,2′-disulfonic acid disodium salt, 4,4′-diazidobenzalacetone-2,2′-disulfonic acid disodium salt, and the like. The compounds described in JP-B-57-43891 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, JP-A-2-929
05, JP-A-2-173007, JP-A-2-20475
0, the compounds described in JP-A-4-26849, JP-A-4-50205 and the like can be used. Further, two or more kinds of these compounds can be mixed and used.

The proportion of the high molecular compound, which is an essential component of the photosensitive composition of the present invention, and the photosensitive compound is preferably 1 to 50% by weight, more preferably 5 to 25% by weight of the photosensitive compound with respect to the high molecular compound. A range of weight% is more preferable. The reason is that if it is less than 5% by weight, the sensitivity of the photosensitive composition becomes poor, and if it is less than 1% by weight, the sensitivity becomes even lower. Further, if it exceeds 25% by weight, the coating property becomes poor, and if it exceeds 50% by weight, it becomes even worse.

To the photosensitive composition of the present invention, another water-soluble polymer compound compatible with the above composition can be added. The reason for adding the water-soluble polymer compound is to improve the characteristics of the photosensitive composition as a coating such as fluidity and coatability, or to improve the characteristics of the coating film. Examples of such polymer compounds include methyl cellulose,
Cellulose such as hydroxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, gelatin,
Examples thereof include, but are not limited to, poly (meth) acrylamide, (meth) acrylamide-diacetone acrylamide copolymer, and (meth) acrylamide-acryloylmorpholine copolymer. Moreover, you may use 2 or more types of these high molecular compounds simultaneously.

To the photosensitive composition of the present invention, ethylene glycol, sorbitol, a surfactant or the like is added for the purpose of improving the paint properties and coating film properties, and vinyl tris (β- Coupling agents such as methoxyethoxy) silane can also be added. In general, it is known that these substances can be added to improve the above-mentioned properties, and they are disclosed in JP-A-48-90185 and JP-A-50-90185.
These are disclosed in 33764.

In the pattern forming method of the present invention, it is necessary to perform exposure under the condition that gaseous oxygen is present. Also,
It is preferable to perform exposure in a range of the Schwarz-Schild's constant p of 0 <p <0.76. Here, regarding the Schwarz-Bartz constant and the reciprocity law failure, the above-mentioned JP-A-48-901 is used.
85, JP-A-50-33764.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be specifically described below by taking a method of manufacturing a cathode ray tube for forming a black matrix pattern on a face panel as an example. The photosensitive composition applied to the face panel is composed of at least a water-soluble polymer as a base resin and a photosensitizer.

In the method of manufacturing a cathode ray tube using the above photosensitive composition, the method of forming the black matrix on the phosphor screen is
A solution prepared by dissolving the above-mentioned photosensitive composition in water to about 1 to 5% by weight is applied to the inner surface of the face panel 1 of the color cathode ray tube so that the photoresist film thickness is 0.1 to 1.0 μm, and dried. Then, the photoresist layer is exposed through the shadow mask 4.

Next, development is performed with water to remove the unexposed portion, and a photo-cured pattern is formed on the inner surface of the face panel 1. Subsequently, the liquid containing the light absorbing substance is applied to the entire inner surface of the face panel 1 and dried. Next, the resist hardened part and the absorptive substance on the resist hardened part are peeled and removed by a lift-off method using a peeling agent to form a black matrix pattern. Further, a red, blue, and green photosensitive paint containing each phosphor is applied in order, dried, solidified by light irradiation, and developed to form each phosphor dot,
The phosphor screen 3 was formed. Below, funnel 2, neck 5,
The electron gun 6 is attached and a color cathode ray tube is manufactured by a usual method. (Example 1) 69.26 g of vinylcaprolactam and 70.74 g of acrylamide were placed in a 2000 ml separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube, and a thermometer.
1860 g of water was taken, and this was dissolved by stirring while purging with nitrogen. This was heated to 60 ° C., and 5 ml of an aqueous solution containing 0.30 g of 2,2′-azobis (2- (2-imidazolin-2-yl) propane) dihydrochloride was added to initiate polymerization. In this state, polymerization was carried out for 4 hours and cooled to obtain a copolymer. In the reaction product thus obtained, almost all the monomers are polymerized. The viscosity of this 1.5 wt% aqueous solution was 21.3 mPa · s and the pH was 7.83.

In this aqueous solution, 10% by weight of 4,4'-diazidostilbene-2,2'-disulfonic acid disodium salt, 100% by weight of ethylene glycol, and a silane coupling agent of 0. 8% by weight was added to obtain a photosensitive composition aqueous solution. This photosensitive composition aqueous solution was spin-coated on the inner surface of a color CRT 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. The sensitivity at that time was 4.1 mJ. Next, spray development was performed for 35 seconds using warm water of 40 ° C. to obtain well-formed negative pattern dots. This photosensitive composition exhibited reciprocity law failure characteristics.

Next, a carbon suspension was applied onto the dots, and 0.10% by weight of hydrogen peroxide and 0.0% of sulfamic acid were added.
A black matrix was formed by removing the dots and carbon on the dots with a 2% by weight peeling solution at 30 ° C. Further, a photosensitive coating material containing each of red, blue and green phosphors was applied in order by a usual method, dried, solidified by light irradiation and developed to form each phosphor dot. Hereinafter, a color CRT was manufactured by a usual method. (Example 2) 31.72 g of vinylcaprolactam, 108.28 g of vinylpyrrolidone and 1860 g of deionized water were placed in the reaction vessel of Example 1 and treated in the same manner as in Example 1. The 2.0% by weight aqueous solution of the obtained copolymer had a viscosity of 17.9 mPa · s and a pH of 6.87. The same photo-crosslinking agent as in Example 1 was added, and the same treatment was performed thereafter.
At this time, the silane coupling agent was added at 0.3% by weight. The sensitivity at that time was 8.2 mJ, and the development was completely completed in 30 seconds. This photosensitive composition also exhibited reciprocity law failure characteristics. The stripping was performed with a stripping solution of 0.15% by weight hydrogen peroxide and 0.05% by weight sulfamic acid at 30 ° C.

Hereinafter, a color cathode ray tube was manufactured by a usual method. (Example 3) Acrylamide 6 was added to the reaction vessel of Example 1.
9.75 g, diacetone acrylamide 27.67 g,
42.58 g of vinylcaprolactam and 1860 g of deionized water were added, and the same treatment as in Example 1 was carried out. The viscosity of a 1.5% aqueous solution of the obtained copolymer is 18.8 mPa.
s and pH were 6.53. The same photo-crosslinking agent as in Example 1 was added, and the same treatment was performed thereafter. At this time, 0.5% by weight of the silane coupling agent was added. The sensitivity at that time is 4.
It was 0 mJ, and the development was completely completed in 30 seconds. This photosensitive composition also exhibited reciprocity law failure characteristics. The stripping was performed with a stripping solution containing 0.12% by weight of hydrogen peroxide and 0.03% by weight of sulfamic acid at 30 ° C.

Hereinafter, a color cathode ray tube was manufactured by a usual method. (Example 4) Acrylamide 3 was added to the reaction vessel of Example 1.
1.87 g, vinylpyrrolidone 49.80 g, vinylcaprolactam 58.33 g and deionized water 186
0 g was added and the same treatment as in Example 1 was performed. The viscosity of a 1.5% aqueous solution of the obtained copolymer is 16.8 mPa · s, p
H was 6.53. The same photo-crosslinking agent as in Example 1 was added, and the same treatment was performed thereafter. At this time, 0.5% by weight of the silane coupling agent was added. The sensitivity at that time is 5.2 mJ
And the development was completely completed in 30 seconds. This photosensitive composition also exhibited reciprocity law failure characteristics. Further, the peeling was performed using 3% of hydrogen peroxide 0.13% by weight and sulfamic acid 0.03% by weight.
The stripping solution was used at 0 ° C.

Hereinafter, a color cathode ray tube was manufactured by a usual method. (Comparative Example 1) 69.55 g of acrylamide and 70.45 of diacetone acrylamide were placed in a 2000 ml separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube, and a thermometer.
g and 1860 g of water were taken, and this was dissolved by stirring while substituting with nitrogen. Heat this to 58 ° C and add it to 2,2 '
-Azobis (2- (2-imidazolin-2-yl) propane) dihydrochloride 0.20 g of an aqueous solution 5 ml was added to initiate polymerization. Polymerization was carried out for 4 hours in this state, followed by cooling to obtain a 7 wt% aqueous solution. In the reaction product thus obtained, almost all the monomers are polymerized. This was diluted to give a 1.5% by weight aqueous solution of the copolymer. The viscosity of this aqueous solution was 19.7 mPa · s and the pH was 5.13.

Thereafter, a photosensitive composition was prepared in the same manner as in Example 1 and then the same operations were carried out to produce a color cathode ray tube by a usual method. The sensitivity at this time was 4.0 mJ. At this time, stripping was performed with a stripping solution containing 0.15% by weight of hydrogen peroxide and 0.05% by weight of sulfamic acid at 40 ° C., but partial stripping was not possible. (Comparative Example 2) Polyvinylpyrrolidone (PVPK90) was used in place of the copolymer of Example 1, a photosensitive composition was prepared in the same manner as in Example 1, and then the same operation was carried out. A cathode ray tube was manufactured. At this time, peeling was performed with 0.15% by weight of hydrogen peroxide and 0.0% of sulfamic acid.
It was carried out with a 5% by weight stripping solution at 40 ° C., but no stripping was possible.

[0034]

As described above, the photosensitive composition of the present invention has excellent exfoliation properties and exhibits reciprocity law failure characteristics. Therefore, there is an effect that it can be efficiently performed, for example, in manufacturing a large-sized black matrix type color CRT. Further, even when used for manufacturing a high-definition black matrix type color CRT, it is possible to manufacture a black matrix having a high contrast.

[Brief description of drawings]

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

[Explanation of symbols]

1 ... Face panel, 2 ... Funnel, 3 ... Phosphor screen, 4
... shadow mask, 5 ... neck, 6 ... electron gun.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Nobuaki Hayashi             Hitachi, Ltd. 3300 Hayano, Mobara-shi, Chiba             Factory Display Group F-term (reference) 2H025 AA01 AA16 AB17 AC01 AD01                       BA06 CB06 CB41 FA39                 2H097 CA12 LA11                 5C028 JJ03

Claims (5)

[Claims] 1. A photosensitive composition comprising a polymer compound containing vinylcaprolactam represented by the following chemical formula 1 and a photosensitive compound. [Chemical 1] 2. A photosensitive composition, wherein the polymer compound according to claim 1 is a copolymer containing one or both or all of acrylamide or diacetone acrylamide or vinylpyrrolidone. 3. The photosensitive composition according to claim 1 or 2, wherein the photosensitive compound is a water-soluble azide compound. 4. A step of forming a coating film of the photosensitive composition having reciprocity law failure property according to claim 1 on the surface on which a desired pattern is to be formed, A pattern forming method comprising: a step of exposing a film to a desired pattern in the presence of oxygen; 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 law failure property on a face panel, and a step of irradiating the coating film with radiation through a shadow mask,
A method of manufacturing a cathode ray tube, comprising the step of developing the coating film with a developing solution, wherein the photosensitive composition comprises:
A method of manufacturing a cathode ray tube, which is the photosensitive composition as described in any one of 1.