JPH0651509A - Photosensitive composition and pattern forming method using the same - Google Patents

Abstract

PURPOSE:To provide a photosensitive compsn. having reciprocity law failure characteristics, excellent photosensitive characteristics and excellent developability. CONSTITUTION:This photosensitive compsn. consists of a water-soluble azido compd. and a polymer of a vinyl monomer having a morpholino group, e.g. acryloylmorpholine or a copolymer of a vinyl monomer having a morpholino group with a water-soluble vinyl monomer, e.g. acrylamide. This photosensitive compsn. has reciprocity law failure characteristics in the presence of oxygen and is suitable for use in the production of the black matrix of a color cathode- ray tube.

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 using the same, and more particularly to a photosensitive composition suitable for producing a fluorescent screen of a color cathode ray tube and a pattern forming method using the same.

[0002]

2. Description of the Related Art As one example of conventional pattern forming methods, JP-A-48-90185 and JP-A-50-33764 describe a method for producing a black matrix of a color cathode ray tube and a photosensitive composition used therefor. . This method uses a photosensitive composition having reciprocity law failure characteristics, for example, a composition comprising a polymer compound such as acrylamide-diacetone acrylamide copolymer and a bisazide-based cross-linking agent, and is substantially smaller than the light irradiation area. This is a method of forming an area pattern.

This will be described in detail. The black matrix type color cathode ray tube is red on the inner surface of the panel,
It has a phosphor pattern such as blue or green phosphor dots or stripes, 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 characteristic 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,
Develop to form dots of the photosensitive composition. Carbon is applied on top of this, and the dots are removed together with the carbon on it with a stripping solution. Thus, black matrix holes are formed. Red, blue, and green phosphor dots are sequentially formed in this hole. Since a photosensitive composition having reciprocity law failure characteristics is used, the area of dots of the photosensitive composition,
That is, the area of the phosphor dots is substantially smaller than the area irradiated with light through the shadow mask. 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 phosphor dot. Therefore, the manufactured color CRT is bright and has excellent contrast.

[0004]

The above-mentioned prior art has a problem that the developing time is long when the above-mentioned photosensitive composition is used. If a photosensitive composition capable of shortening the developing time without deteriorating other properties is obtained, not only the working time can be shortened but also the hot water for development can be saved. An object of the present invention is to provide a photosensitive composition having reciprocity law failure characteristics, excellent photosensitivity characteristics, and excellent developability, and a pattern forming method using the same.

[0005]

The photosensitive composition of the present invention for achieving the above object comprises (1) a polymer of a vinyl monomer having a morpholino group or a vinyl monomer having a morpholino group. It is composed of a water-soluble vinyl monomer copolymer and (2) a water-soluble azide compound. Examples of the vinyl monomer having a morpholino group include acryloylmorpholine (hereinafter abbreviated as ACMO) and methacryloylmorpholine (hereinafter abbreviated as MACMO).

Examples of water-soluble vinyl monomers include acrylamide (hereinafter abbreviated as AA), diacetone acrylamide (hereinafter abbreviated as DAA), methacrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, acrylamide propane sulfonic acid. , Vinylpyrrolidone, vinyl methyl ether, vinyl alcohol and the like. 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, the monomer in the copolymer has a formal structure (eg vinyl alcohol).
If it is the same as the case of polymerizing, the monomer is treated as being included in the water-soluble vinyl monomer. These polymers or copolymers are added to an aqueous solution of a monomer in 2.2 '.
-Azobis (2-amidinopropane) hydrochloride or a persulfate such as potassium persulfate or ammonium persulfate, or a redox catalyst using these can be polymerized or copolymerized to be synthesized.

Before investigating the composition ratio of the preferred monomer of the above copolymer, the following explanation will be given. The photosensitive composition of the present invention has reciprocity law failure properties, to which a polymer portion of a vinyl monomer having a morpholino group contributes. On the other hand, in the case of DAA which is a water-soluble vinyl monomer, its polymer portion also contributes to the reciprocity law failure characteristic. Therefore, it is preferable to divide the water-soluble vinyl monomer into DAA and others and to determine the ratio of them to the vinyl monomer having a morpholino group. In the above copolymer, the amount of the water-soluble vinyl monomer other than DAA with respect to the vinyl monomer having a morpholino group is preferably in the range of 0.1 to 10.0 in terms of monomer ratio, and 0.2 The range of 2 is more preferable. When it is 10.0 or less, the reciprocity law failure characteristic of the photosensitive composition is improved, and when it is 2 or less, it is further improved. Further, if it is less than 0.1, the photosensitivity is deteriorated, and if it is less than 0.2, the film properties are slightly changed.

When DAA is added to the copolymer,
The ratio of the DAA monomer to the vinyl monomer having a morpholino group is preferably 0.01 to 2.0,
The range of 0.1 to 2.0 is more preferable. When the amount of DAA is 0.01 or more, the reciprocity law failure characteristic is improved, and when 0.1 or more, the reciprocity failure characteristic is further improved. A water-soluble vinyl monomer other than DAA may be used together with DAA, and the amount of the water-soluble vinyl monomer other than DAA at that time is within the same range as described above.

The water-soluble azide compound also includes polymers and copolymers having an azide group. Examples of such water-soluble azide compounds include 4,4′-diazidostilbene-2,2′-disulfonic acid disodium salt and 4,4′-
The compounds described in JP-B-57-43891 such as diazidodibenzalacetone-2,2'-disulfonic acid disodium salt can be used. Further, maleic acid-4-vinyl monoazitobenzylidene acetophenone sodium sulfonate copolymer and the like are disclosed in JP-A-1-302348.
The copolymers described in 1. can be used. Further, JP-A-2-92905, JP-A-2-173007,
The compounds described in JP-A-2-204750, JP-A-4-26849, JP-A-4-50205 and the like can be used. Of these water-soluble azide compounds, those having two or more azido groups in one molecule are preferable. Furthermore, two or more kinds of these compounds can be mixed and used. These water-soluble azide compounds are preferably used in the range of 1 to 50% by weight, more preferably 5 to 20% by weight, based on the polymer or copolymer.
If the water-soluble azide compound content is less than 1%, the sensitivity is not sufficient,
On the other hand, if it exceeds 50%, the properties of the film when formed into a coating film are not preferable.

In addition to the above-mentioned polymer or copolymer, a water-soluble polymer compound having compatibility therewith can be added to the photosensitive composition of the present invention. The reason for adding such a high molecular compound is to improve the characteristics of the coating composition such as the fluidity and coatability of the aqueous solution when the composition is made into an aqueous solution for forming the photosensitive composition into a coating film, or This is for improving the characteristics of the film. These polymer compounds are added in a range that does not significantly affect the photosensitivity such as reciprocity law failure characteristics of the photosensitive composition or does not affect at all. Therefore, the amount of the polymer compound is preferably in the range of 1 to 50% by weight, and preferably 1 to 20% by weight, based on the polymer or copolymer.
Is more preferable. Examples of such polymer compounds include polyvinyl alcohol and polyacrylamide, which are disclosed in Japanese Patent Publication No. 57-43891. As this polymer compound, an acrylamide / diacetone acrylamide copolymer (hereinafter abbreviated as AA / DAA copolymer) which has been used in a conventional photosensitive composition having reciprocity law failure characteristics may be used. In this case, the amount is preferably in the range of 1 to 100% by weight, and more preferably in the range of 1 to 20% by weight, based on the polymer or copolymer.

In addition to the above-mentioned polymer or copolymer, ethylene glycol, sorbitol, a surfactant or the like can be added to the photosensitive composition of the present invention in order to improve coating characteristics and coating characteristics. In general, it is well known that these substances are added to improve the above characteristics, and these are disclosed in JP-B-57-43891, JP-B-52-20225 and the like. The photosensitive composition of the present invention is
A small amount of an adhesion promoter such as vinyltris (β-methoxyethoxy) silane can be added to improve the adhesion between the coating film and the glass. These adhesion promoters are disclosed in JP-B-57-43891, JP-B-52-20225 and the like. The pattern forming method of the present invention requires exposure under conditions where oxygen is present in the film. Further, it is preferable that the Schwarz-Schild constant p is exposed in the range of 0 <p <0.76. The Schwarz-Schild's constant and the reciprocity law failure characteristic are described in JP-B-57-43891.

[0012]

The photosensitive composition of the present invention well absorbs the excitation light emitted from the ultra-high pressure mercury lamp, especially the light having wavelengths of 365, 405 and 436 nm. Further, since the polymer or copolymer used in the photosensitive composition of the present invention has a morpholino group, when the photosensitive composition is formed into a coating film, the coating film has good oxygen permeability. . Therefore, the photosensitive composition of the present invention exhibits reciprocity law failure characteristics, and a pattern with good contrast can be obtained. In addition, since the morpholino group is water-soluble, it has a higher solubility in water than conventional photosensitive compositions. Therefore, the photosensitive composition of the present invention is more soluble than conventional photosensitive compositions and can be developed in a shorter time than conventional ones.

[0013]

EXAMPLES The present invention will be described in detail below with reference to examples. The results are shown in Table 1 together with the comparative example. A typical result showing the reciprocity law failure characteristic is shown in FIG. Example 1 AA (25.9 g) and DAA2 were placed in a 2 liter reaction vessel equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas introducing tube.
6.2g, ACMO 21.8g (AA / DAA / ACM
O molar ratio 2.35 / 1/1) and ion-exchanged water 930g
Was charged, and while maintaining the temperature at 58 ° C., the air in the apparatus was replaced with nitrogen gas, and 10 ml of a 1% 2, 2-azobis (2-amidinopropane) hydrochloride aqueous solution was added. The reaction solution was kept at 58 ° C. for 6 hours while stirring and then taken out from the reaction vessel. In the reaction product thus obtained, almost all the monomers are polymerized. This was diluted to give a 1.5% aqueous solution of the copolymer. The viscosity of this aqueous solution is
It was 22.0 cp.

4,4'-as a photocrosslinking agent in this aqueous solution.
Diazidostilbene-2,2'-disulfonic acid disodium salt was added to 10% by weight of the copolymer to prepare a photosensitive composition aqueous solution. This photosensitive composition aqueous solution was spin-coated on the inner surface of a color cathode ray tube face plate to a thickness of 0.5 to 0.8 μm, and dried to form a coating film. Using a shadow mask and using an ultra-high pressure mercury lamp as a light source, UV exposure was performed for 20 seconds at an illuminance of 1.43 W / m ² . Next, when development was carried out for 33 seconds with a hot water spray at a water temperature of 40 ° C., the development was completely completed, and dots of the photosensitive composition were obtained. The photosensitive composition also showed reciprocity law failure characteristics. Then, the carbon suspension was applied onto the dots, and the dots and the carbon on the dots were removed by a stripping solution to form a black matrix. Further, a photosensitive coating material containing each of red, blue, and green phosphors was applied in order, dried, solidified by light irradiation, and developed to form each phosphor dot. Hereinafter, a color CRT was manufactured by a usual method. In the production of the copolymer, the same number of moles of MACMO was used instead of ACMO, and the copolymer was synthesized and treated in the same manner as above, but almost the same result was obtained.

Comparative Example 1 Using an acrylamide / diacetone acrylamide copolymer (AA / DAA molar ratio of 2.35), 4,4'-diazidostilbene-2,2'-disulfonic acid diester was prepared in the same manner as in Example 1. Sodium salt was added to obtain a conventional photosensitive composition aqueous solution. Then, it processed like Example 1. In this case, it took 40 seconds to completely complete the development.

Example 2 23.4 g of AA and ACMO4 were added to the reaction vessel of Example 1.
6.6 g (AA / ACMO molar ratio of 1) and 930 g of ion-exchanged 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 was 22.3 cp. The same photo-crosslinking agent as in Example 1 was added, and the same treatment was performed thereafter. The development was completely completed in 30 seconds. This photosensitive composition also showed reciprocity law failure characteristics. A copolymer was synthesized using MACMO in the same number of moles instead of ACMO, and treated in the same manner as above, but almost the same result was obtained.

Example 3 To the copolymer of Example 2 was added a copolymer of vinyl azidocinnamylidene acetophenone sulfonic acid sodium salt and maleic acid sodium salt as a photo-crosslinking agent to prepare a photosensitive composition aqueous solution, Thereafter, the same treatment as in Example 1 was performed.
However, UV exposure was performed for 20 seconds at an illuminance of 0.4 W / m ² . Development was completely completed in 33 seconds. The photosensitive composition also exhibited reciprocity law failure characteristics.

Comparative Example 2 The photocrosslinking agent of Example 3 was added to the copolymer of Comparative Example 1 and treated in the same manner as in Example 3. In this case, it took 50 seconds to complete the development.

Example 4 In the reaction vessel of Example 1, 14.0 g of AA, ACMO56.
0 g (AA / ACMO molar ratio of 0.5) and 930 g of ion-exchanged water were added, and the same treatment as in Example 1 was performed. The viscosity of a 1.5% aqueous solution of the obtained copolymer was 21.1 cp. The photo-crosslinking agent of Example 3 was added, and then the same treatment as in Example 3 was carried out. The development was completely completed in 32 seconds. The photosensitive composition also exhibited reciprocity law failure characteristics.

Example 5 10.0 g of AA, ACMO60.
0 g (AA / ACMO molar ratio 0.33) and 930 g of ion-exchanged 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 was 20.3 cp. The photo-crosslinking agent of Example 3 was added, and then the same treatment as in Example 3 was carried out. Development was completed in 28 seconds. The photosensitive composition also exhibited reciprocity law failure characteristics. The result showing this reciprocity law failure characteristic is shown in FIG. This reciprocity law failure characteristic has almost the same tendency as the reciprocity law failure characteristic of the conventional photosensitive composition shown in Comparative Example 1.

Example 6 6.4 g of AA and 63.6 of ACMO were placed in the reaction vessel of Example 1.
g (AA / ACMO molar ratio 0.2) and ion-exchanged water 9
30 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 19.7 cp. The photo-crosslinking agent of Example 3 was added, and then the same treatment as in Example 3 was carried out. Development was completed in 25 seconds. The photosensitive composition also exhibited reciprocity law failure characteristics.

Example 7 In the reaction vessel of Example 1, 35.2 g of AA, ACMO34.
8 g (AA / ACMO molar ratio 2) and ion-exchanged water 93
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 was 22.5 cp.
The photo-crosslinking agent of Example 3 was added, and then the same treatment as in Example 3 was carried out. Development was completely completed in 35 seconds. The photosensitive composition also exhibited reciprocity law failure characteristics.

Example 8 In the reaction vessel of Example 1, 42.2 g of AA, ACMO27.
8 g (AA / ACMO molar ratio 3) and ion-exchanged water 93
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 was 23.0 cp.
The photo-crosslinking agent of Example 3 was added, and then the same treatment as in Example 3 was carried out. The development was completely completed in 37 seconds. The photosensitive composition also exhibited reciprocity law failure characteristics.

Example 9 AA (50.0 g), ACMO20.
0 g (AA / ACMO molar ratio 5) and ion-exchanged water 93
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 was 23.6 cp.
The photo-crosslinking agent of Example 3 was added, and then the same treatment as in Example 3 was carried out. The development was completely completed in 40 seconds. The photosensitive composition also exhibited reciprocity law failure characteristics.

Example 10 22.0 g of AA and 26.2 g of DAA were added to the reaction vessel of Example 1.
g, ACMO 21.8 g (AA / DAA / ACMO molar ratio 2/1/1) and ion-exchanged water 930 g were added and treated in the same manner as in Example 1. The viscosity of a 1.5% aqueous solution of the obtained copolymer was 22.5 cp. The photo-crosslinking agent of Example 3 was added, and then the same treatment as in Example 3 was carried out. Development is 43
Completed in seconds. The photosensitive composition also exhibited reciprocity law failure characteristics.

Example 11 16.8 g of AA and 20.0 DAA were added to the reaction vessel of Example 1.
g, ACMO 33.2 g (AA / DAA / ACMO molar ratio 2/1/2) and ion-exchanged water 930 g 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 was 22.0 cp. The photo-crosslinking agent of Example 3 was added, and then the same treatment as in Example 3 was carried out. Development is 39
Completed in seconds. The photosensitive composition also exhibited reciprocity law failure characteristics.

Example 12 AA 9.8g, DAA 11.6 in the reaction vessel of Example 1.
g, ACMO 48.6 g (AA / DAA / ACMO molar ratio 2/1/5) and ion-exchanged water 930 g were added and treated in the same manner as in Example 1. The viscosity of a 1.5% aqueous solution of the obtained copolymer was 21.2 cp. The photo-crosslinking agent of Example 3 was added, and then the same treatment as in Example 3 was carried out. Development is 35
Completed in seconds. The photosensitive composition also exhibited reciprocity law failure characteristics.

Example 13 70.0 g of ACMO and 930 g of ion-exchanged water were placed in the reaction vessel of Example 1 and treated in the same manner as in Example 1. The viscosity of a 1.5% aqueous solution of the obtained copolymer was 21.6 cp. The photo-crosslinking agent of Example 3 was added, and then the same treatment as in Example 3 was carried out. The development was completely completed in 37 seconds. Also,
This photosensitive composition exhibited reciprocity law failure characteristics.

[0029] ☆

Table 1 Table 1 Example No. Copolymer 1.5% viscosity (cp) Development time (sec) 1 22.0 33 2 22.3 30 3 Same as above 33 4 21.1 32 5 20.3 28 6 19.7 25 7 22.5 35 8 23.0 37 9 23.6 40 10 22.5 43 11 22.0 39 12 21.2 35 13 21.6 37 Comparative Example 1 20.6 40 Comparative Example 2 Same as 50 * Example 14 Example 3 The photosensitive composition aqueous solution was spin-coated on a silicon substrate to form a coating film having a thickness of 1 μm. After drying, it was exposed through a mask with a mercury-xenon lamp. Then, after developing with water, it was rinsed with acetone. The sensitivity was 20 mJ. A negative pattern having a line width of 1 μm was obtained on a silicon substrate.

Example 15 The aqueous solution of the photosensitive composition of Example 3 was applied onto an aluminum substrate twice using a roll coater. After drying, it was exposed through a mask with a mercury-xenon lamp. Then, after developing with water, it was rinsed with acetone. 1 μm on aluminum substrate
A negative pattern having a line width of

Example 16 Example 14 was changed to Example 14 by replacing the aluminum substrate of Example 15 with a copper substrate.
The same operation was performed and the same result was obtained.

Example 17 The photosensitive composition aqueous solution of Example 3 was spin-coated on a glass substrate. After drying, it was exposed with a high pressure mercury lamp through a mask and then developed with water. This was dyed with a water-soluble red dye. The same operation was performed for green and blue dyes to obtain a color filter on a glass substrate.

Example 18 The photosensitive composition aqueous solution of Example 3 was spin-coated on the protective film on the silicon device. After drying, it was exposed with a high pressure mercury lamp through a mask and then developed with water. This was dyed with a water-soluble cyan dye. The same operation was performed on the yellow dye to obtain a color filter on the silicon device.

[0034]

The photosensitive composition of the present invention has excellent developing characteristics and exhibits reciprocity law failure characteristics. Therefore, there is an effect that development can be performed with a small amount of water in a short time, for example, for use in manufacturing a large 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 diagram showing the relationship between exposure time and exposure illuminance for explaining the reciprocity law failure characteristic of the photosensitive composition of the present invention.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical indication location G03F 7/30 7124-2H H01J 9/14 H 7354-5E (72) Inventor Nobuaki Hayashi 1 Higashi Koikeku, Kokubunji, Tokyo 280-chome Co., Ltd. Central Research Laboratory, Hitachi, Ltd. (72) Inventor Small ▲ High ▼ Yoshiyuki Yoshino, 1-5-1, Marunouchi, Chiyoda-ku, Tokyo Electronic Device Division, Hitachi, Ltd. (72) Inventor Masahiro Nishizawa Chiba Prefecture 3300 Hayano, Mobara-shi Hitachi Ltd. Mobara factory

Claims (11)

[Claims] 1. A polymer of a vinyl monomer having a morpholino group, a copolymer of a vinyl monomer having a morpholino group and a water-soluble vinyl monomer, and a water-soluble azide compound. Photosensitive composition. 2. The photosensitive composition according to claim 1, wherein the vinyl monomer having a morpholino group is at least one monomer selected from the group consisting of acryloylmorpholine and methacryloylmorpholine. A characteristic photosensitive composition. 3. The photosensitive composition according to claim 1 or 2, wherein the water-soluble vinyl monomer is acrylamide. 4. The photosensitive composition according to claim 3, wherein the amount of the water-soluble vinyl monomer constituting the copolymer is 0. 1 with respect to the vinyl monomer having a morpholino group. A photosensitive composition, which is in the range of 1 to 10.0. 5. The photosensitive composition according to claim 1, wherein the water-soluble vinyl monomer is composed of two or more kinds of monomers, one of which is diacetone acrylamide and the other of which is A photosensitive composition comprising a water-soluble vinyl monomer other than diacetone acrylamide. 6. The photosensitive composition according to claim 5, wherein the water-soluble vinyl monomer other than the diacetone acrylamide is acrylamide. 7. The photosensitive composition according to claim 5 or 6, wherein the amount of diacetone acrylamide constituting the copolymer is 0.01 to a vinyl monomer having a morpholino group in a monomer ratio. The amount of the water-soluble vinyl monomer other than diacetone acrylamide is 2.0.
A photosensitive composition characterized in that the monomer ratio is in the range of 0.1 to 10.0 with respect to the vinyl monomer having a morpholino group. 8. The photosensitive composition according to any one of claims 1 to 7, wherein the water-soluble azide compound is a compound having two or more azide groups in one molecule. Sex composition. 9. The photosensitive composition according to any one of claims 1 to 8, wherein the amount of the water-soluble azide compound is in the range of 1 to 50% by weight based on the polymer or copolymer. A photosensitive composition which is characterized by being: 10. A step of forming a coating film of the photosensitive composition according to any one of claims 1 to 8 on a surface on which a desired pattern is to be formed, A pattern forming method comprising: a step of performing a desired pattern exposure in the presence of oxygen; and a step of developing the coating film to form a pattern having an area substantially smaller than a light irradiation area. 11. The pattern forming method according to claim 10, wherein the surface is an inner surface of a face plate of a color cathode ray tube.