JPS5915246A - Photosensitive composition and formation of pattern - Google Patents

Abstract

PURPOSE:To form a positive type pattern enabling the manufacture of the black matrix of a color picture tube by a simple method, by using a novel water-soluble positive type photosensitive composition. CONSTITUTION:A substrate is coated with a water-soluble photosensitive composition consisting of a water-soluble aromatic diazonium salt, water-soluble phenol, a water-soluble high-molecular compound and a deliquescent inorg. salt such as zinc chloride, magnesium chloride, calcium chloride, lithium chloride, zinc bromide, magnesium bromide or lithium bromide as a binder. The resulting film is exposed to chemical radiation through a prescribed pattern. Powder is brought into contact with the exposed film, and an alkaline gas or liq. is further brought into contact with the film to develop the film.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive composition and a method of forming a pattern using the same. More specifically, the present invention relates to a bond type photosensitive composition applied to copying optical figures, linography, etc., and a method for forming a positive pattern using the same.

Hitherto, no water-soluble Bong-type photosensitive composition has been found. Some are known to be soluble in organic solvents, but
``It has been difficult to use it in large quantities industrially due to the danger of fire due to its solvent and its toxicity to the human body.''

For example, in order to form a black matrix on the inner surface of the face plate of a color picture tube, it is possible to form the black matrix by a simple method using a water-based positive photosensitive composition. Since there is no composition, it is carried out by complicated methods such as attaching.

That is, a water bath solution of a water-soluble negative photosensitive composition is applied to the inner surface of a color picture tube face plate, dried, exposed, developed, dried, and then a carbon dispersion is applied, dried, the photosensitive composition is peeled off, and the drying process is performed. The process is complicated, and a large amount of 1:1 is required for developing and stripping the photosensitive composition.
There were problems such as the need for water for catfish.

Purpose of the invention CJ, new falcon water bathing 1 no 1 position 71;! +Providing a method for forming a pattern of positive lql+ with photosensitive phase formation materials and kumquats.

Another object of the present invention is the expression 'i t'i'-nanoJ7,
1. Provided is a method for forming a bong-shaped pattern using a water-bathable positive-working photosensitive composition 1 which can be used to produce a black matrix for a picture tube. There is a particular thing.

In order to solve the above-mentioned problem, the inventors of the present invention and others, in order to solve the above-mentioned problem, we have requested the following:
In this paper, we proposed a water-soluble carbon-type photosensitive composition consisting of a water-soluble aromatic/anonium salt, a water-soluble phenol, and a water-soluble polymer compound.

The photosensitive composition of the present invention is an improved version of the photosensitive composition described in 1- above.

The photosensitive composition of the present invention is characterized by comprising a water-soluble aromatic diazonium salt, a water-soluble phenol, a water-bathable polymer compound, and an adhesive.

It is preferable to use a deliquescent inorganic salt as the adhesive, such as lead chloride, magnesium chloride, chloride, lithium chloride, lead bromide, magnesium/lambide bromide, and lithium bromide. Among these, zinc chloride id is particularly preferred.

When the photosensitive composition of the present invention is used to form a powder layer thereon, the powder layer can be firmly adhered with high density or density.

The method for forming a positive pattern of the present invention is to apply a water-bathable photosensitive composition comprising a water-bathable aromatic diazonium salt, a water-soluble phenol, a water-soluble polymer compound, and an adhesive onto a substrate to form a coating film. First step.

a second step of irradiating the coating film with actinic radiation having a predetermined pattern and misting it; a fifth step of bringing the powder into contact with the exposed coating film; a step of applying an alkaline gas to the coating film after contacting the powder; Alternatively, it is characterized by comprising a fourth step of bringing the liquid into contact with each other and a fifth step of developing the coating film after the fourth step.

As a water-soluble aromatic diazonium salt, it is described in the above-mentioned earlier application, and in the same 4% t as the water-soluble aromatic diazonium salt, 4-(tumethylamino)penzenediazonium chloride/salt chloride, 4-(diethylamino)'\nse7 Noanium chloride/chloride [11<lead, %'-(N-edyl-N-hydrochloride/ethylamine)/s//sosonium chloride/zinc chloride, 4-(trimethylamino)-6-medquinobenzene(Tzoni) Umu chloride/zinc chloride, 4-methoxy/be/ze//ryozoniumuk01) de-zinc chloride, 4-(phenylryomino)be/sendiazonium-acidic sulfate, 4-(
Used are dimethylamino) ben7anediazonium-detrafluoroborate, 4-(diethylamino)be/zendiazonium-tetrafluoroborate, and the like.

Among these, the diazonium salts listed No. 1, No. 2, No. 5 and No. 6 are particularly clever.

Two or more types of these diazoniums can be used in combination.

Examples of water-based 71-nols include polyhydric phenols or their derivatives such as hydroxy-71, catechol, resolun, pyrogallonic acid, sodium 2-naphthol-4-sulfonate, and 2-naphthol-4. ，
5-disulfonoic acid distriuno, etc. are used.

Among these, polyhydric phenols or derivatives thereof, such as evahydroquinone, catechol, phenol, pyrogallol, are particularly preferred. Two or more types of phenols can be mixed.

As water-soluble polymer compounds, polyvinylpyrrolid/,
Acrylamide/diacetone acrylamide copolymer,
Acrylamide/diacetone acrylamide/2-acrylamide-2-methylpropanesulfonic acid copolymer,
Acrylamide/diacetone acrylamide/methacrylic acid copolymer, hydroquinepropyl/methylcellulose, polyacrylamide, polyvinyl alcohol, gelatin, polyethylene oxide, and copolymers and derivatives of these polymeric compounds that exhibit water d properties, etc. It is.

Examples of derivatives include polyvia and a partially acetalized product of luano-col.

Among these, water-soluble polymer compounds 1 listed in #1, #2, #6, and #4 are particularly preferred. These water-soluble polymer compounds 1, of course, 2 or more types-1
The two can be used in combination.

The adhesive is an aromatic sia/uno salt ((on the other hand, the range of 05 to 20 is li [shi<, 2 to 1).
A range of 0 is more desirable.

If the amount of adhesive is small, the I of the powder will not be 1 minute, and the adhesion strength will not be as high. This is because if there is a large amount of crumbling adhesive, it will not dry within 1 minute due to its deliquescent nature, and the adhesive strength between the film and the substrate will be weak, causing the entire adhesive to peel off and crumble during development.

Phenols have a power in the range of 01 mol to 1.5 mol per 1 mol of aromatic/azonium salt; It is preferable for the salt ratio to be in the range of O5 to Otsu, and even more preferable to be in the range of 1 to 6.

Sensitivity can be changed by changing the type of diazonium salt. However, the sedimentation has little effect on the amount of powder deposited.

This photosensitive composition is applied to a substrate to form a coating film, and this (/
If a pattern is exposed using actinic radiation such as ultraviolet rays and exposed to an alkaline gas or liquid such as ammonia vapor, and then washed with water, the unexposed areas of the coating become insoluble or poorly soluble in water. While the coating remains on the substrate, the exposed portion of the coating film is completely removed from the substrate, forming a pattern.

Furthermore, the following methods can be used to form a powder pattern using the photosensitive composition of the present invention. That is, by bringing powder into contact with the exposed coating film, then contacting it with preferably an alkaline gas or liquid, and washing with water, a pattern is obtained in which powder is deposited on unexposed areas. Therefore, carbon can be used as powder to form one part of the face plate of a color picture tube.

It is preferable to use substantially dry powder as the powder.

The process of contacting the powder with the coating film is preferably carried out in the middle of the process of exposing the powder to the coating film (11) and bringing the alkaline gas or liquid into contact with the coating film. If this is done, the powder will absorb and scatter the J. This is because if this is done, the coating film in the unexposed areas will harden and the amount of powder deposited will decrease.

It is preferable to use alkaline vapor or liquid in the form of dregs such as ammonia gas or organic amine gas. If alkaline liquid such as aqueous ammonia is used, the reaction may be delayed if the concentration of the mixture is low. The coating film begins to deteriorate before the acid reaction progresses.On the other hand, when the acid concentration is high, the reaction progresses unevenly.This is because sufficient care must be taken to control the acid reaction.

In the method of the present invention, the reason why there is a difference in the solubility of a photosensitive composition film between the unexposed area and the exposed area is thought to be obvious. In the unexposed areas of the coating film, when the atmosphere becomes alkaline with ammonia, a reaction occurs in which diazonium compound 1 reacts with phenol to produce a water-insoluble or poorly water-soluble substance. In the paint film of the exposed area, such reaction is only slight due to the reduction of diazonium compounds due to exposure.
Or maybe it's just one thing that doesn't happen at all.

The main reactions between azonium salts and phenols in an alkaline atmosphere are coupling reactions and redox reactions.

Among the above-mentioned phenols, resolun and 2-naphthol derivatives mostly cause only a coupling reaction.

Hydroquino/, on the other hand, only undergoes redox reactions. It is believed that the cleaved catechol, pyrogallol and gallic acid undergo both a coupling reaction and a redox reaction.

Any of the above reactions produces compound 1 which is insoluble in water. At this time, if a water-bathable polymer compound 1 coexists, the whole or a part of the polymer compound becomes insoluble in water. The mechanism is thought to be that the polymer compound and the above-mentioned non-water-bathable reaction product have good compatibility, and a homogeneous mixture of the two is formed, or that it is incompatible with water.

Hereinafter, the present invention will be explained more specifically using examples, and the effects of the present invention σ) will be illustrated using comparative examples.

EXAMPLE An aqueous solution according to the present invention having the following composition was prepared.

p-Noacy N-Ethyl-N- Hydroquinoethylaniline chloride Zinc chloride ・・036yhydroginono ・0117y Acrylamide + AA+ ・Nyose]・/Acrylamide (DAAI conjugate (composition ratio 65:55) -0,59 Chloride Salivary lead 1.27 water
...587
If this water bath solution is applied to a 6 on x 6 cm crow,
The coating was applied by spinning at the rotation speed of Orpm and dried with hot air to form a film. Approximately 50cm was applied to this coating from a 500W ultra-high pressure mercury lamp.
At a distance, irradiate the light from a mercury lamp for 40 seconds through the Yadu mask.

At the same time, graphite powder (Hitachi Powder Metallurgical Hitazol GP-
72B+ was sprinkled onto the coating film and allowed to adhere. This coating film was exposed to steam generated from concentrated ammonia water for about 5 seconds, and then washed with water. By this operation, graphite adheres only to the unexposed portions of the glass plate surface, forming a black film.

The light transmittance of the graphite coating portion before washing with water was 0.04%, and the light transmittance after washing with water was 0.5%. This is sufficient to compare with the light transmittance of 8% after washing with water and 15% after washing with water, when no adhesive such as instant lead chloride is added in Comparative Example 1, which will be described below. The value is small and there is little change in value before and after washing with water, indicating that the black coating has a high density of graphite and strong adhesive strength.

Comparative Example 1 A water bath solution was prepared which was not according to the present invention and had the following composition:

p-diano-N-ethyl-N-hydroquinoethylaniline chloride zinc chloride 056yhydroquinone 011yAA-DAA copolymer (composition ratio 65:55) ・05 water
・
When the same operation as in Example 1 was carried out using 1m of this water, graphite was deposited only on the unexposed portions of the surface of the glass plate to form a black film.

The transmittance (C) of the graphite coated portion before washing with water was 8%, but it became 15% after washing with water.

Example 2 Water R4m according to the present invention having the following composition was prepared.

p-/azo N-ethyl-N- Hydroquinoethylaniline chloride 1F lead chloride...0.36SI
.

Hydroquinone ・011yAA-
DA/12-7 chloride/l/7 mitoh 2-methylbroylene sulfonic acid (AMPS + covalent combination (composition ratio 57°34°9) ・0.57 lead chloride 0.8p water
・581
A similar black film was obtained by carrying out the same operations as in Example 1, except that this aqueous solution f was used and mankan dioxide powder (-grade reagent manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) was used in place of the graphite powder in Example 1.

The light transmittance of the black coating AiJ after washing with water was 1%, and the light transmittance after washing with water was 2%.

Example 3 Magnetochloride/IIF lead chloride in Example 1 was replaced with
The same operation as in Example 1 was performed except that a ram was used to obtain a similar black film.

The light transmittance of the black coating before washing with water was 1%, and the light transmittance id of the black film after washing with water was 4%.

Example 4 An aqueous solution according to the present invention having the following composition was prepared (
-It is.

p-thiaso N, N-/edylanili/chloride zinc chloride ・036y hydroquinone 011y poly N-vinylpyrrolide. Manufactured by FGAF I (-90+ ・0.5
P lead bromide...toy water
29] Using this aqueous solution, the same operation as in Example 1 was performed to obtain a similar black film.

The actual transmittance of the black film part before washing with water is 1%, and the light transmittance after washing is 4% or 49 points.

Example 5 A water bath solution according to the present invention having the following composition was prepared.

p-Diazo-N, N-7 Methylaniline chloride Lead chloride ・・066y resol/n ・・016 Nopoly N-vinylpyrrolid 10.59 Zinc bromide °1・2 No water
・28
Using this aqueous solution, the same operation as in Example 2 was carried out to obtain 11 g of black manganese dioxide powder deposited on the unrefined portion.

The water washing AiJ of the black film and the light transmittance after washing were both equivalent to those of Actual Mq Example 2.

Unfortunately, we conducted a test using catechol instead of Renolun, and the results were almost the same.

Example 6 The same amount of pyrogallol was used in place of the hydroquinone in Example 2, and the same operation as in Example 2 was carried out to obtain a similar black wave 11Q.

The light transmittance of the black film of water-washed Ail was 3%, and that after water-washing was 5%.

Furthermore, the same results were obtained when 0.241 of 2-naphthol-4-sulfonic acid was used instead of pyrogallol.

Example 7 A water bath solution according to the present invention having the following composition was prepared.

p-/Azo N-Ethyl-N- Pidroquine Zyl Aniline Chloride ll1i Lead Chloride 0
66yl Nidrogyno 7 -0.1
1.7 Hydroxy7propyl methylcellulose (Shin-Etsu Chemical Metrose 60SHlo, 3y Lidium Chloride 167 Water
58yUsing this water bath solution, the same procedure as in Example 1 and 4J was carried out to obtain a black film in which graphite was deposited only on the unexposed areas.

The expected transmittance of Black Wave 11Q before washing with water was 12%, and that after washing with water was 5%.

However, using lithium bromide instead of lithium chloride showed similar results.

Example 8 A water bath solution according to the present invention having the following composition was prepared/c.

p-Diazo-N, N-diethylaniline chloride zinc chloride 056y catechol ・o, +i9! Acrylic limide/diacetone acrylamide/methacrylic acid copolymer (composition ratio 58:55 near) -0,5y
Salt f Hikaru/1 l, -1,5 no water
...5JzUsing this aqueous solution, the same operation as in Example 1 was performed to obtain a similar black coating.

The light transmittance of the black film of the water-washed AiJ was 6%, and the V value after washing was 6%.

one! In addition, when Magnebromide/Rum was used in place of Cal/Rum in No. 11, similar results were obtained.

Example 9 - Instead of the acrylamide/diacetone acrylamide copolymer of Example 1, polyvinyl alcohol (Poval 224 manufactured by Kuraray) was used as 071, and the same operation as in Example 1 was carried out to obtain a similar black film. .

The light transmittance of the black film of AiJ washed with water was 2%, and that after washing with water was 6%.

Example 10 An aqueous solution 11 according to the present invention having the following composition was prepared.

p-Diazo-N-phenylaniline acidic sulfate '0.301hydroginone 011yvol)' (
N-vinylpyrroliton) 05 lead chloride
0.89 water
29y Using this aqueous solution, the same operation as in Example 1 was carried out except that the exposure time was 9 D seconds, and the same black film was obtained.

The apparent permeability V of the black film before washing with water was 4%, and after washing with water it was 6%.

Example 11 Example 2 except that triiron tetroxide (-grade reagent manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) was used instead of manpower dioxide in Example 2.
A similar black film was obtained by performing the same operation as above.

The expected 1j4 pass rate of the black film before and after washing with water is the same as that of Example 2.

Actual sister example + VXJ6 Instead of graphite, trioxide
A similar black film was obtained by carrying out the same operation as in Example 1, except that KRUTO ('-grade reagent manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) was used.

The light transmittance of the black film before washing with water was 1%, and the light transmittance after washing with water was 2%.

Similar results were obtained by using cobalt oxide (-grade reagent manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) or molybdenum disulfide (Hitasol MD-2081 manufactured by Nippon Sγ Powder Metallurgy Co., Ltd.) instead of tricobalt tetraoxide.

As is clear from the description in (a) below, and especially as can be seen from Comparison 1 of the above Examples and Comparative Examples, the water bathable positive photosensitive composition of the present invention and the positive pattern formation using the same The law has shown extremely significant effects.

Representative Patent Attorney Junnosuke Nakamura

Claims (1)

[Scope of Claims] (1) A water-soluble bomb-type photosensitive composition comprising a water-soluble aromatic diazonium salt, a water-soluble phenol, a water-soluble polymer compound, and an adhesive. (2) The photosensitive composition according to claim 1, wherein the adhesive is a compound selected from the group consisting of deliquescent inorganic salts, and at least at least one kind of compound. (6) The above adhesive is zinc chloride, macne/umum chloride,
The photosensitive composition according to claim 1, which is at least one compound selected from the group consisting of chloride, lithium chloride, zinc bromide, magnesium bromide, and lithium bromide. (4) The water bathable phenols are polyhydric phenols,
7. The photosensitive composition according to claim 1, which is at least one compound selected from the group consisting of derivatives thereof and naphthol derivatives. (5) The water-bathable phenolics listed in (5) are hydroquinone, catechol, cylindrical lunone, hyrocalol, gallic acid, 2-
naphthol-4-sulfmenate, 2-naphthol-4
The photosensitive composition according to any one of claims 1 to 6, which is at least one compound selected from the group consisting of , 5-disulfanoic acid salts. (6) The water-soluble polymer compound is polyhinylpyrrolidone, acrylamide/diacetone acrylamide copolymer, acrylamide/diacetone acrylamide/2-
Acrylamide-2-methylpropanesulfonic acid copolymer, acrylamide/diacetone acrylamide/methacrylic acid copolymer, hydroxypropyl/methylcellulose, polyacrylamide, polyvinyl alcohol,
Claim 1, which is at least one polymeric compound selected from the group consisting of water-soluble compounds of gelatin, polyethylene oxide, and copolymers or derivatives thereof.
The photosensitive composition according to any one of Items 1 to 5. Claims 1 to 6, wherein the amount of the ejaculation adhesive is in the range of 0.05 to 2.0% by weight of the above-mentioned water-soluble aromatic diazo; The photosensitive composition according to any one of the above. (8) The amount of the water-soluble phenol is 0.1 to 1 mole per mole of the water bathable aromatic diazonium salt.
．． The photosensitive composition according to any one of claims 1 to 7, wherein the amount is in the range of 5 mol. (9) The amount of the water-soluble polymer compound is in the range of 0.05 to 0.05 by weight with respect to the total amount of the water-soluble phenols and the water-soluble aromatic diazonium salt. The photosensitive composition according to any one of the dimensions from item 1 to item 8. (10) The above water-soluble aromatic diazonium salts include 4-(dimethylamino)benzenediazonium chloride/zinc chloride, 4-(diethylamine)benzenediazonium-
Chloride/zinc chloride, 4-(N-ethyl-N~hydroxy7ethylamino)benzenediazonium chloride/zinc chloride, 4-(diethylamine)-5-methoxy/bense/dianonium chloride/zinc chloride, 4- Metoki/
B/C/N azonium tarolito/zinc chloride, 4-()
℃nylamino)benzene/diazonium-it sulfate, 4-(dimethylamino)henona/diazonium-tetrafluoroborate, 4-i/6-thylamino)benzene/azonium-tetrafluoroborate The photosensitive composition according to any one of claims 1 to *9, which is at least one diazonium salt selected from the group consisting of: (11) The first step of applying a water-soluble photosensitive composition comprising a water-soluble aromatic di-azonium salt, a water-soluble phenol, a water-soluble polymer compound, and an adhesive onto a substrate to form a coating film; A second step of irradiating and exposing the paint film with actinic radiation having a predetermined pattern, a third step of bringing the powder into contact with the exposed paint film, and a third step of bringing the powder into contact with the exposed paint film; A fourth step of contacting an alkaline gas or liquid, and the fourth step described above.
A positive pattern forming method comprising a fifth step of developing the coated film after the step. (12) The pattern forming method according to claim 11, wherein the adhesive is at least L compound selected from the group consisting of deliquescent inorganic salts. (13) The adhesive is at least one compound selected from the group consisting of zinc chloride, magne/rum chloride, cal/rum chloride, lithium chloride, lead bromide, magne/rum bromide, and lithium bromide. A pattern forming method according to claim 11. (14) The water-soluble phenol is at least one compound selected from the group consisting of polyhydric phenonopes derivatives and naphthol derivatives, according to any one of claims 11 to 16 of the claim 12fI. pattern formation method. (15) The water-soluble phenols are hydroquinone, catechol, resolunon, hyrogallol, gallic acid, 2-naphthol-4-sulfonate, 2-naphthol-4,
The method for forming a pattern according to any one of claims 11 to 16, wherein the pattern forming method is at least one compound selected from the group consisting of 5-disulfate. (16) The water-soluble polymer compound may be polyvinylpyrrolidone, acrylamide/acetone acrylamide copolymer, acrylamide/acetone acrylamide copolymer, or acrylamide/acetone acrylamide copolymer.
2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylamide/acetone acrylamide 7-methacrylic acid copolymer, hydroquinepropyl methylcellulose, polyacrylamide, polyvinyl alcohol, celadine, polyethylene oxide, and copolymers thereof The pattern forming method according to claim 11 to +5Jfi, wherein the pattern forming method is at least two polymeric compounds selected from the group consisting of water-bathable compounds or derivatives. (17) The adhesive has an I11α range of 0.5 to 20 in weight ratio with respect to the water bathable aromatic diazonium salt, according to any one of claims 11m to 16. Pattern formation method. (18) The amount of the water-soluble phenol described above is 71 moles per mole of the water-soluble aromatic diazonium salt, and from 01 moles to 1 mole.
Claim 11 or 1'-) in the range of 5 moles.
The pattern forming method according to any one of the 17th erotic techniques. (19) The amount of the water bathing polymer compound is different for the combination of the water-soluble phenol and the water-soluble aromatic diazonium tray, and the weight ratio is in the range of 05 to 6. The method for forming the putter 7 according to any one of the dimensions in the range 11 to 18. (20) The above water-soluble aromatic diazonium salt, 4-
(dimethylamino) penzendiazonium chloride.
Zinc chloride, 4-(diethylamine)penthe/diazonium-chloride/zinc chloride, 4-(N-ethyl-N-hydroquinethylamino)penzenediazonium chloride/zinc chloride, 4-(dimethylamino)-6-med Quinobenzenediazonium chloride/zinc chloride, 4-methoxy/he/sendiazonium chloride/mj lead chloride, 4-
(phenylamino)benzenediazonium-H (iR
H+a, at least one diazolam salt selected from the group consisting of 4 (dimethylamine) pensene diazonium-tetrafluoroborate, 4-(/ethyl-amino)be/cene diazonium-tetrafluoroporate; A method for forming Baku-7 according to any one of claims 11 to 19. (21) The fourth step is carried out by contacting with an alkaline gas.
The pattern forming method described in Isuwa and Kani from Items 1 to 20. (22) The pattern forming method according to any one of claims 11 to 21, wherein the alkaline gas is ammonia scum. (23) -J- The pattern forming method according to any one of claims 11 to 21, wherein the alkaline gas is a 41-mer amine gas. (24) Graphite, diacid (f2
7/ Any one of claims 11 to 23 which is a black powder consisting of gun, triiron tetroxide, cobalt oxide, tricobalt tetroxide, silver sulfide, lead sulfide or -molybdenum sulfide.・ζ turn formation method described in .