JP3044500B2 - Method of forming black matrix - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming a black matrix, and more particularly, to a method of forming a black matrix having an excellent pattern shape.
The present invention also relates to a method for easily forming a black matrix having excellent resolution.

[0002]

2. Description of the Related Art In preparing a black matrix of a color cathode ray tube, a method of forming a graphite pattern as a material of the black matrix on a glass substrate is to apply a coating solution of a water-soluble photopolymer on the glass substrate and dry the coating. After that, irradiate with actinic rays through a shadow mask, and then develop and dry with water to form a photo-cured pattern on the glass substrate, apply a graphite slurry over the entire surface, dry, and then use a release agent. In general, a method of forming a black matrix on a glass substrate by dissolving and removing the photo-cured pattern and removing the graphite slurry on the photo-cured pattern portion, followed by washing.

A water-soluble photopolymer used for forming a black matrix is composed of a polyvinyl alcohol and a dichromate, or is composed of a water-soluble polymer and a water-soluble bisazide compound. Those composed of alcohol and dichromate have a problem that the change in sensitivity is large, the resolution is poor, and a graphite pattern having an excellent pattern shape cannot be formed. In addition, those composed of a water-soluble polymer and a water-soluble bis azide compound have excellent resolution but low sensitivity, and further have poor adhesion to a glass substrate, so that a water-soluble silane coupling agent must be added. There is a problem, and also has a problem that sufficient release can not be performed with a known release agent, hot hydrogen peroxide, as a result, high resolution, a pattern having an excellent pattern shape can not be formed, When a black matrix is formed using these water-soluble polymers, it is not possible to obtain an excellent pattern shape and resolution, which makes it difficult to apply to a high-definition television that requires an ultra-fine display. Development of a method of forming a black matrix having excellent resolution is strongly desired.

[0004]

SUMMARY OF THE INVENTION The inventors of the present invention have conducted intensive studies for the purpose of providing a method of forming a black matrix which has solved the above-mentioned problems. By using a water-soluble photopolymer, it was found that the purpose could be achieved,
The present invention has been made.

[0005]

According to the present invention, a photocurable pattern is formed on a substrate by using a water-soluble photopolymer, then a graphite slurry is applied over the entire surface and dried, and then the photocurable pattern is formed by using a release agent. In the method of forming a black matrix on a substrate by removing the compound, the water-soluble photopolymer is represented by the following general formulas (I) and (II)

[0006]

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[0007]

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[0008] It is an object of the present invention to provide a method for forming a black matrix, which is a polymer compound having a structural unit represented by the following formula:

Hereinafter, the present invention will be described in detail. The water-soluble photopolymer used in the method of the present invention is a polymer compound having the structural units represented by the above-mentioned general formulas (I) and (II), and the one represented by the general formula (I) is an alcoholic compound composed of vinyl alcohol. Structural units containing a hydroxyl group, and those represented by the general formula (1I) are structural units containing an azidocinnamoylsulfonic acid group. The polymer compound having these two constitutional units exhibits excellent properties not found in the conventional water-soluble photopolymer. One is excellent in adhesion to a glass substrate, the other is high sensitivity, and the third is excellent in peelability.

The water-soluble photopolymer used in the method of the present invention is synthesized by synthesizing a non-photosensitive water-soluble polymer and then introducing a photosensitive group into a side chain of the polymer.
Specifically, after vinyl acetate and diacetone acrylamide are copolymerized using an azobis-based polymerization initiator, the reaction solution is appropriately diluted, and an alkali is added to hydrolyze the acetic acid group to form a hydroxyl group. Separate and purify, dissolve in pure water. Then, dissolve sodium 4-azidobenzaldehyde-2-sulfonate in the obtained aqueous solution, add warm, add alkali, and add diacetone acrylamide unit in the copolymer. Carbonyl group and 4-azidobenzaldehyde-
A coating solution of a water-soluble photopolymer is prepared by introducing an azido group into a water-soluble polymer by an aldol condensation reaction with an aldehyde group of sodium 2-sulfonate. If necessary, pure water may be added to the coating liquid for the purpose of adjusting the viscosity, and various known additives may be added.

The water-soluble photopolymer used in the method of the present invention has the structural units represented by the above general formulas (I) and (II), and has various properties depending on its structural ratio, degree of polymerization and amount of photosensitive group introduced. More specifically, the charged molar ratio in the copolymerization is in the range of 1 to 100 mol, preferably 20 to 60 mol of vinyl acetate per 1 mol of diacetone acrylamide. The degree of polymerization is from 300 to 3,000, preferably from 500 to 2,000. The photosensitive group is introduced in an amount of 10 to 90 mol%, preferably 20 to 80 mol%, based on the amount of diacetone acrylamide. The degree of saponification of the vinyl acetate group is 20
９９99 mol%, preferably 70-90 mol%.

As described above, the water-soluble photopolymer of the present invention is synthesized by synthesizing a non-photosensitive water-soluble polymer and then introducing a photosensitive group into a side chain of the polymer. By introducing an aldehyde through an acetalization reaction in an aqueous solution, a water-soluble polymer is obtained which can obtain a pattern having extremely excellent water resistance, and is preferably used. In this case, the aldehydes that can be introduced by the acetalization reaction include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, and crotonaldehyde, benzaldehyde, N-dialkylbenzaldehyde, alkylbenzaldehyde, and cinamic aldehyde. And heterocyclic aldehydes such as pyridine aldehyde. Further, aldehydes include 4-azidobenzaldehyde-2-sulfonic acid and its water-soluble salts, formylstyrylpyridine and its quaternized salts.
These aldehydes can be used alone or in combination of two or more. Those preferably used in practical use are propionaldehyde, n-butyraldehyde,
Crotonaldehyde, and n-butyraldehyde is most preferably used.

In the acetalization reaction with aldehydes, it is preferable to acetalize not more than 15 mol% of the total hydroxyl groups of the water-soluble polymer, and if it exceeds 15 mol%, a water-soluble polymer having excellent stability cannot be obtained, which is not preferable. . In this case, the degree of polymerization of the water-soluble polymer to be synthesized is in the range of 100 to 3000, preferably 500 to 2500.

Although the water-soluble photopolymer used in the method of the present invention is exemplified by a water-soluble polymer composed of a copolymer of vinyl acetate and diacetone acrylamide as described above, in the synthesis of the water-soluble polymer, As long as the object of the present invention is not impaired, a multi-component copolymer to which known water-soluble monomers such as acrylic acid and acrylamide are added, or a mixture with other water-soluble polymers may be used.

In particular, the dissolution and releasability can be improved by blending polyvinyl alcohol or modified polyvinyl alcohol as another water-soluble polymer. in this case,
The polyvinyl alcohol and the modified polyvinyl alcohol only need to show water solubility, and either partially saponified products or completely saponified products can be used. Examples of the modified polyvinyl alcohol include various modified polyvinyl alcohols such as those modified with diacetone acrylamide, acryloylmorpholine, N-vinyl-2-pyrrolidone, and those having a silicon-containing group added to a side chain. These may be used alone or in combination of two or more.

The water-soluble photopolymer used in the method of the present invention is advantageously used in the form of a coating solution, and a solution prepared by dissolving a synthesized water-soluble photopolymer in water, pure water, an alkaline aqueous solution or the like is used. .

Next, an example of the method of the present invention will be described. A coating solution of the above-mentioned water-soluble photopolymer is applied on a glass substrate, dried, and then selectively irradiated with an actinic ray through a mask using an ultra-high pressure mercury lamp or the like. And then tap water,
The non-irradiated portion of the active light beam is dissolved and removed with pure water and dried to form a photo-cured pattern on the glass substrate. Next, a graphite slurry is applied on the substrate, dried, and then the photo-curing pattern is removed with a release agent, and the graphite slurry on the photo-cured pattern portion is removed and washed to form a black pattern comprising a graphite pattern on a glass substrate. A matrix is formed.

The method of the present invention is characterized in that a specific water-soluble photopolymer is used. The release agent used for releasing the photocurable pattern formed from such a water-soluble photopolymer is, for example, hydrogen peroxide. Although well-known release agents can be used satisfactorily, it is particularly preferable to use an acidic aqueous solution of periodic acid or a water-soluble salt thereof because the complete release treatment can be performed very easily. Specifically, 3 to 15% by weight maintained at 20 to 30 ° C
By completely immersing the film in a periodic acid aqueous solution, a complete peeling treatment without film residue can be performed. Further, the temperature may be increased to the above temperature.

[0019]

EXAMPLES The present invention will now be described specifically with reference to examples, but is not limited thereto.

Example 1 Vinyl acetate 100 g, diacetone acrylamide 10
g, 2,2'-azobis- as an azobis-based polymerization initiator
0.1 g of (2,4-dimethylvaleronitrile) is dissolved in 100 g of methyl alcohol, put into a 500 ml separable flask, heated by a mantle heater with a reflux condenser, boiled, reacted for 3 hours, and sealed for half a day. I left it.

Then, the obtained reaction solution was added to 1 liter of methyl alcohol and stirred, and then a solution of 5 g of sodium hydroxide dissolved in 100 ml of methyl alcohol was added. The mixture was reacted for 1 hour with stirring, and the mixture was centrifuged. The resin precipitated in the reaction solution was separated, washed with methyl alcohol, and then dissolved in pure water to obtain a resin content of 2% by weight.
2 kg of a water-soluble polymer solution was obtained.

Next, the water-soluble polymer solution is cooled to 40 ° C., 15 g of sodium 4-azidobenzaldehyde-2-sulfonate is dissolved, 10 g of a 10% by weight aqueous sodium hydroxide solution is added, and the mixture is reacted at room temperature for 3 hours. , 50
The mixture was heated to ℃ and reacted for 3 days.

Next, the reaction solution is cooled, neutralized with dilute sulfuric acid, and filtered to obtain a water-soluble photopolymer solution (having a viscosity of 2).
0 cP / 25 ° C.).

This solution is applied as a coating solution on a washed glass substrate by spin coating at 200 rpm and dried to form a coating solution.
An 8 μm thick coating was formed. Then, it was passed through an 8 mm thick soda glass plate with an ultra-high pressure mercury lamp,
After exposure with 0 nm light at an irradiation amount of 20 mJ / cm ² , development with pure water and drying were performed to obtain a photocured pattern on a glass substrate.

A graphite slurry GA-66S (manufactured by Hitachi Powdered Metals Co., Ltd.) was spin-coated at 200 rpm on the substrate,
Dry at 30 ° C. for 30 minutes. Next, the film was immersed in a 5% by weight aqueous solution of periodic acid (23 ° C.) for 2 minutes, and then subjected to water spray cleaning. As a result, a black matrix composed of a graphite pattern having good pattern shape and excellent resolution was formed.

Example 2 500 g of methyl alcohol was placed in a two-liter three-necked flask equipped with a reflux condenser and heated and boiled with a mantle heater. Then, 80 g of diacetone acrylamide, 120 g of vinyl acetate and 2,2, a radical polymerization initiator, 2 '
-Azobis- (2,4-dimethylvaleronitrile)
After dropping the mixed solution with 0.2 g over 1 hour, 2
After 2, 4 and 24 hours, 2,2'-
Azobis- (2,4-dimethylvaleronitrile)
The reaction was terminated after 48 hours by adding 2 g of 10 ml methyl alcohol solution, diluted by adding 500 g of methyl alcohol, transferred to a 3 liter beaker, heated to 55 ° C., and agitated with 25% by weight of sodium hydroxide. After adding 10 g of a methyl alcohol solution and stirring for 4 hours, the precipitate was separated by filtration, washed with methyl alcohol, and dried by blowing at 40 ° C. to obtain 200 g of a dry resin. The polymerization degree of this resin was about 500.

Then, the obtained resin was dissolved by heating in 4 kg of pure water and heated to 50 ° C., and 60 g of sodium 4-azidobenzaldehyde-2-sulfonate was added and dissolved.
After adding 30 g of a 0% by weight aqueous sodium hydroxide solution and reacting for 1 day, the mixture was cooled to room temperature, neutralized with dilute hydrochloric acid, and filtered to obtain a solution having a solid content of 5.7% by weight. Next, a solution obtained by diluting this solution twice with pure water was applied as a coating solution to a degreased glass plate by spin coating, dried at 50 ° C. and 0.5 μm
, A negative mask was brought into close contact with the film, and a 5 mm-thick glass plate was passed over the negative mask with an ultra-high pressure mercury lamp at 3 mJ /
Exposure to cm ² was performed, followed by development by pouring on pure water, staining with an aqueous solution of methyl violet, and drying, to obtain a pattern faithful to a negative mask.

The colloidal graphite solution Hitasol GA-6
6M (manufactured by Hitachi Powdered Metals Co., Ltd.) 2-fold diluted solution at 200 rpm
And dried at 50 ° C. for 30 minutes. Next, the film was immersed in a 5% by weight aqueous solution of periodic acid (25 ° C.) for 1 minute, and washed with water spray. As a result, a black matrix composed of a graphite pattern having a good pattern shape and excellent resolution was formed.

Example 3 Pursen water was added to the solution having a solid content of 5.7% by weight obtained in Example 2 to make up to 3.0% by weight, and 10 parts by weight of a solution of polyvinyl alcohol, Gohsenol EG-40 (Japan) was added. A pattern was formed in the same operation as in Example 2 using a mixture of 10 parts by weight of a 3% by weight aqueous solution of Synthetic Co., Ltd.) as a coating liquid, and a pattern faithful to the mask was obtained. Next, when a graphite pattern was formed by the same operation as in Example 2, the pattern shape was good and the resolution was excellent.

Example 4 Pure water was added to the solution having a solid content of 5.7% by weight obtained in Example 2 to make up to 3.0% by weight, and 10 parts by weight of the silicon-containing polyvinyl alcohol R-1130 ( Using a mixture of 10 parts by weight of a 3% by weight aqueous solution of Kuraray Co., Ltd. as a coating solution, a pattern was formed by the same operation as in Example 2. A pattern faithful to the mask could be formed, and peeling of the pattern was also confirmed. However, a pattern having excellent adhesion was obtained. Further, when a graphite pattern was formed by the same operation as in Example 2, the pattern shape was excellent and the resolution was excellent.

Example 5 500 ml of methyl alcohol was placed in a 2 liter flask and heated to boiling. 150 g of vinyl acetate, 50 g of acryloylmorpholine and 2,2'-azobis-
(2,4-dimethylvaleronitrile) A mixture of 0.2 g with the mixture was added dropwise over 2 hours, and reacted for 24 hours.
Then add 500 ml of methyl alcohol and dilute,
After cooling to room temperature, transfer to a 5 liter beaker, add 50 ml of a 10 wt% sodium hydroxide in methyl alcohol solution with stirring, and further stir for 3 hours.
The precipitate is taken out by filtration, washed with 500 ml of methyl alcohol, and dried by blowing at 40 ° C. to obtain a polymerization degree of about 6%.
Thus, 100 g of a modified polyvinyl alcohol modified with acryloylmorpholine No. 00 was obtained.

Then, 5.7% by weight of the solid content obtained in Example 2
A solution was prepared by adding 10 parts by weight of the above-mentioned modified polyvinyl alcohol to 10 parts by weight of a solution prepared by adding pure water to the above solution to 3.0% by weight. As a result, a pattern faithful to the mask was obtained. Next, when a graphite pattern was formed by the same operation as in Example 2, the pattern shape was good and the resolution was excellent.

Example 6 500 ml of methyl alcohol was placed in a 2 liter flask and heated to boiling, and 150 g of vinyl acetate and N-
Vinyl-2-pyrrolidone and 2,2'-azobis- (2,
A mixture of 0.2 g of 4-dimethylvaleronitrile) was added dropwise over 1 hour, and the mixture was reacted for 48 hours. At this time, 0.1 g of 2,2'-azobis- (2,4-dimethylvaleronitrile) was added after 6 hours, 12 hours and 24 hours from the start of the reaction. Then after cooling to room temperature 5
Transfer to a liter beaker and stir 10% by weight
After adding 50 ml of sodium hydroxide in methyl alcohol solution and stirring for further 3 hours, the precipitate was taken out by filtration, washed with 500 ml of methyl alcohol, and washed with 500 ml of methyl alcohol.
By drying with air at 0 ° C., 90 g of modified polyvinyl alcohol modified with N-vinyl-2-pyrrolidone having a degree of polymerization of about 500 was obtained.

Next, 5.7% by weight of the solid content obtained in Example 2
A solution was prepared by adding 10 parts by weight of the above-mentioned modified polyvinyl alcohol to 10 parts by weight of a solution prepared by adding pure water to the above solution to 3.0% by weight. As a result, a pattern faithful to the mask was obtained. Next, when a graphite pattern was formed by the same operation as in Example 2, the pattern shape was good and the resolution was excellent.

Example 7 500 g of methyl alcohol was placed in a two-liter three-necked flask equipped with a reflux condenser and heated with a heating mantle to boil.
g, 240 g of vinyl acetate and 0.2 g of 2,2'-azobis- (2,4-dimethylvaleronitrile) as a radical polymerization initiator were added dropwise over 1 hour.
2,2 'after 2 hours, 4 hours and 24 hours respectively
10 ml of methyl alcohol in which 0.2 g of -azobis- (2,4-dimethylvaleronitrile) was added and dissolved was added and reacted for 4 hours.

Then, 500 g of methyl alcohol is added to the reaction solution, transferred to a 3 liter beaker, heated to 55 ° C., 10 g of a 25% by weight sodium hydroxide in methyl alcohol solution is added with stirring, and the mixture is stirred for 4 hours and filtered. The resulting resin was separated, washed with methyl alcohol, and dried by blowing air at 40 ° C.
g of dry resin was obtained. This resin had a polymerization degree of about 1500 and a saponification degree of about 98 mol%.

Next, the obtained resin was dissolved by heating in 4 kg of pure water, heated to 50 ° C. and dispersed by adding 14 g of n-butyraldehyde, and 10 ml of a 20% by weight aqueous sulfuric acid solution was added thereto and reacted for 3 hours. Next, a 10% by weight aqueous sodium hydroxide solution was added for neutralization, and 4-azidobenzaldehyde-2 was added.
-50 g of sodium sulfonate was added and dissolved, 30 g of a 10% by weight aqueous sodium hydroxide solution was added, and the mixture was reacted for 24 hours. After cooling to room temperature, neutralized with dilute hydrochloric acid, and filtered to obtain a solid content of 5.7% by weight. A solution was obtained. Then add this solution to 2
The diluted solution was spin-coated on a degreased glass plate as a coating solution, dried at 50 ° C. to obtain a 1 μm film,
A negative mask was adhered, and a 3 mm J / cm ² exposure was performed with an ultra-high pressure mercury lamp through a glass plate having a thickness of 5 mm, followed by shower development with pure water for 10 seconds. The pattern was formed, no peeling of the pattern was confirmed, and the pattern was excellent in adhesion. The obtained pattern did not swell, no swelling of the pattern was observed, and the pattern was excellent in water resistance.

Next, when a graphite pattern was formed by the same operation as in Example 2, it was found that the pattern shape was excellent and the resolution was excellent.

[0039]

According to the method for forming a black matrix of the present invention, the use of a water-soluble photopolymer having a specific structural unit makes it possible to easily form a black matrix excellent in pattern shape and resolution. This is an extremely practical forming method that can be applied to high-definition televisions and the like that require a fine display.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C09K 11/02 C09K 11/02 Z G03F 7/012 501 G03F 7/012 501 (56) References JP-A-2-92905 (JP) JP-A-59-49278 (JP, A) JP-A-63-72030 (JP, A) JP-A-52-33471 (JP, A) U.S. Pat. No. 3,373,319 (US, A) (58) (Int.Cl. ⁷ , DB name) H01J 9/227 C08F 216/06 C08F 220/60 C08F 299/00 C09D 129/04 C09K 11/02 G03F 7/012

Claims (2)

(57) [Claims] 1. A photocurable pattern is formed on a substrate using a water-soluble photopolymer, and then a graphite slurry is applied over the entire surface and dried, and then the photocurable pattern is removed using a release agent. In the method of forming a black matrix thereon, the water-soluble photopolymer is represented by the following general formulas (I) and (II): Embedded image A method for forming a black matrix, which is a polymer compound having a structural unit represented by: 2. The method for forming a black matrix according to claim 1, wherein the release agent is an acidic aqueous solution of periodic acid or a water-soluble salt thereof.