JPH09185164A - Water-soluble photosensitive resin composition and method for forming black matrix pattern by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a photocured pattern efficiently at high sensitivity in a short exposure time and small exposure by using at least one of polyvinyl pyrrolidone and a copolymer of vinylpyrrolidone and vinylimidazole for a water-soluble polymer. SOLUTION: The water-soluble photosensitive resin composition comprises at least more than one of the water-soluble polymer selected from among polyvinyl pyrrolidone and a copolymer of vinylpyrrolidone and vinylimidazole, and as the photosensitive polymer a polymer composition of a specified structural unit is used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble photosensitive resin composition which is particularly useful for producing a black matrix used for a fluorescent screen of a color cathode ray tube and a method for forming a black matrix pattern using the same. Specifically, it is highly sensitive and has excellent adhesion to a glass substrate, and it is possible to form a pattern in a thin film, and an easily peelable water-soluble photosensitive resin composition, and a black matrix pattern using the same. It relates to a forming method.

[0002]

2. Description of the Related Art A black matrix used for a phosphor screen of a color cathode ray tube of a color television or the like is usually formed by forming a black matrix made of a light-absorbing substance (such as graphite) on a glass panel in a predetermined pattern.
A portion other than the pattern portion forms many small holes (black matrix holes) or stripes (black stripes). Then, the black matrix holes or stripes are usually filled with three primary color phosphors of red (R), green (G) and blue (B) to form three primary color phosphor dots (pattern).
Emitting an electron beam from an electron gun, passing this beam through a large number of through-holes formed in a shadow mask, and selectively stimulating the phosphor dots to emit light to form a color image on the panel. It has become.

In such a shadow mask type color cathode ray tube, each phosphor dot formed on the inner surface of the glass panel and a through hole (electron beam passage hole) of the shadow mask.
If the positional correspondence relationship of is deviated, the electron beam does not hit the target phosphor or hits another phosphor, and the color reproducibility deteriorates. Therefore, in the pattern formation of the black matrix, it is necessary to form the black matrix hole or the stripe portion on the inner surface of the glass panel while maintaining the positional relationship which exactly corresponds to the through hole of the shadow mask. for that reason,
Generally, a shadow mask itself used for a color cathode ray tube is used as an exposure mask used when forming a black matrix pattern. Usually, in such a black matrix pattern formation, first, a water-soluble photosensitive resin composition is applied to the inner surface of the panel to form a photoresist layer, and the exposed portion of the photoresist layer is photocured through a shadow mask, After developing to remove the non-exposed portion to form a photo-cured pattern, a light-absorbing substance is applied over the entire surface of the photo-cured pattern and the exposed substrate and dried to form a black film. Next, the above-mentioned photo-curing pattern is peeled and removed, and the black film on the photo-cured pattern is also peeled and removed to form a black matrix pattern in which matrix holes or stripes are formed at positions corresponding to the through holes of the shadow mask.
Then, the matrix hole or stripe is filled with any one of the three primary color phosphors of red (R), green (G), and blue (B) to form a three primary color phosphor pattern, thereby forming a phosphor screen. Is being made.

As the water-soluble photosensitive resin composition used for forming the black matrix pattern, a polyvinyl alcohol-dichromate-based one, or a water-soluble polymer-water-soluble bis-azide compound-based one has hitherto been used. Has been done.

However, in the polyvinyl alcohol-dichromate system, the change in sensitivity increases with time,
In addition, the resolution is poor, and further, after the exposure is stopped, a dark reaction causes an increase in cross-linked regions, which is a problem. Therefore, if three exposures, developments, and fillings are performed in order to sequentially form a three-primary-color phosphor pattern, the light radiated to the photoresist layer will overlap between the patterns, and should be separated in nature. There is a problem that a phenomenon called so-called docking is likely to occur, in which phosphor patterns of other adjacent colors are continuous. Such a problem has been a serious problem especially in the gap exposure in which the mask is exposed without separating it from the photoresist layer.

In order to avoid this docking phenomenon, for example, in JP-A-48-79970, polyvinylpyrrolidone is used as a water-soluble polymer of a water-soluble photosensitive resin composition of a water-soluble polymer-water-soluble bisazide compound system. A method is disclosed. That is, when polyvinylpyrrolidone is used, when the light irradiation integrated value is less than a certain value, the resulting crosslinking hardly progresses (“reciprocity law failure characteristic”). Therefore, the profile of the crosslinking degree of the photoresist layer is Has a steep slope at a position relatively close to the center of the beam passage hole, and the degree of crosslinking significantly decreases as the distance from the center increases. Therefore, the degree of cross-linking near the outer edge of the beam passage hole does not reach the minimum degree of cross-linking required to form dots, the diameter of the resulting dot is smaller than the diameter of the beam passage hole, and docking does not occur. . However, this JP-A-48-
The water-soluble polymer-water-soluble bisazide compound-based compound as disclosed in Japanese Patent Publication No. 79970 has excellent resolution but low sensitivity, and further has poor adhesion to a glass substrate. It is necessary to add a certain amount or more of an adhesion improver such as an agent, and if the photoresist layer is not formed to a certain thickness or more, a pattern outflow will occur during development, so the photoresist layer cannot be thinned. There is a problem in terms of manufacturing efficiency and manufacturing cost. Further, the photoresist layer is not completely removed at the time of peeling, and peeling residue occurs. Therefore, in the phosphor formation in the next step, the phosphor adheres to this peeling residue, which causes a problem of color mixing.

In addition to the above, a system in which a photosensitive group is introduced into a water-soluble polymer has been proposed as a product excellent in pattern shape and resolution, but this has problems in sensitivity and stability, and is practically used. It has not been realized.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and its object is to provide a photoresist with high sensitivity and a short exposure time, which is particularly used for producing a black matrix such as a color cathode ray tube. A water-soluble photosensitive resin composition capable of efficiently forming a photo-cured pattern with a small exposure amount, excellent in adhesion to a glass substrate, capable of pattern formation even in a thin film, and easily peelable, and It is to provide a method for forming a black matrix pattern using the.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that the water-soluble polymer in a water-soluble photosensitive resin composition of a water-soluble polymer-photosensitive component is used as the water-soluble polymer. The above problems can be solved by using at least one selected from polyvinylpyrrolidone and a copolymer of vinylpyrrolidone and vinylimidazole and further using a polymer compound having a specific constitutional unit as a photosensitive component. Based on this finding, the present invention has been completed.

That is, the present invention provides the following general formula (I)

[0011]

Embedded image In the water-soluble photosensitive resin composition containing a polymer compound having a structural unit represented by the formula (wherein X represents Na, K or NH ₄ ) and a water-soluble polymer, the water-soluble polymer is polyvinyl. A water-soluble photosensitive resin composition comprising at least one selected from the group consisting of pyrrolidone and a copolymer of vinylpyrrolidone and vinylimidazole.

In the present invention, a photo-curing pattern is formed on the substrate by using the water-soluble photosensitive resin composition, a light-absorbing substance is applied to the entire surface, and after drying, the photo-curing pattern and the photo-curing pattern thereon are formed. A method for forming a black matrix pattern, in which a black matrix pattern is formed by peeling and removing a light absorbing substance.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The water-soluble polymer used in the present invention comprises at least one of polyvinylpyrrolidone and a copolymer of vinylpyrrolidone and vinylimidazole, and at least one water-soluble polymer substance which is compatible with them. It may also include a mixture in which the seed is further blended. The above "vinylpyrrolidone" means N-vinyl-2-pyrrolidone, and "vinylimidazole" is an N-vinyl body,
It includes all isomers such as 2-vinyl and 4-vinyl.

The content of vinylimidazole in the copolymer of vinylpyrrolidone and vinylimidazole is selected in the range of 5 to 90 mol% based on 100 mol% of the copolymer. If the content is less than 5 mol%, sufficient releasability cannot be obtained and peeling residue occurs, which causes color mixing when forming the phosphor. For those having a vinyl imidazole content of more than 90 mol%, it is difficult to obtain a water-soluble polymer (copolymer) having a high degree of polymerization (molecular weight) from the viewpoint of synthesis, and only a low molecular weight one is actually obtained. However, when a water-soluble polymer having a low molecular weight is used, the sensitivity of the photosensitive resin composition is generally low. Therefore, it is preferable to use a copolymer having a high molecular weight. From the above points, the vinyl imidazole content is 5 to 90 mol%, preferably 5 to 50 mol%, particularly 10 to 25 mol% based on 100 mol% of the copolymer, and the peelability and sensitivity are good. Is shown and preferred.

Polyvinylpyrrolidone having a high molecular weight is also preferably used for the above reason.

The K value of these water-soluble polymers is 30 to 1
Those of 00, preferably 50 to 100, and particularly 60 to 95 are suitably used. Here, the K value is a value that depends on the molecular weight, and is expressed by the following formula 2

[0018]

[Equation 2] (Wherein C represents the number of grams of the polymer contained in 100 ml of the water-soluble polymer aqueous solution; η _r represents the relative viscosity of the polymer), and the relational expression is satisfied. In the above mathematical formula, the relative viscosity (η _r ) is the specific viscosity of the solution with respect to the solvent, and the viscosity of a solution of a certain concentration (here, a solution of 1 g of the water-soluble polymer in 100 ml of water) is η, When the viscosity of the solvent is η _o , the relative viscosity (η _r ) is calculated by η _r = η / η _o . If the K value exceeds 100, the viscosity becomes too high, which makes it difficult to control the photoresist film thickness, and also reduces the releasability. On the other hand, when the K value is less than 30, the photocurability is lowered and it becomes difficult to form a desired photocurable pattern.

Examples of the above water-soluble polymer substances include carboxymethyl cellulose, hydroxymethyl cellulose, sodium salt of poly-L-glutamic acid, gelatin, polyacrylamide, polyvinyl methyl ether, polyvinyl alcohol, polyvinyl acetal, polyethylene oxide, etc. Polymers or copolymers such as acrylamide-diacetone acrylamide copolymers, acrylamide-vinyl alcohol copolymers, maleic acid-vinyl methyl ether copolymers and the like can be used.

As the polymer compound (photopolymer) having the structural unit represented by the above general formula (I) which is another essential constituent, for example, diacetone acrylamide and other monomers, preferably water-soluble monomers are known. Although it can be obtained by introducing at least one selected from 4-azidobenzaldehyde-2-sulfonic acid and salts thereof into the water-soluble polymer (base polymer) obtained by copolymerization by the method described above by an aldol condensation reaction. The synthesizing method is not limited to this.

Here, examples of the other monomer include acrylic acid, methacrylic acid, dimethylacrylamide, diethylacrylamide, acryloylmorpholine, dimethylaminoethylacrylamide, N-vinyl-2-pyrrolidone, and the like. Acrylic acid and its water-soluble salts, methacrylic acid and its water-soluble salts, dimethylacrylamide, acryloylmorpholine and the like are preferable. Further, vinyl acetate that produces an alcoholic hydroxyl group by a hydrolysis reaction after copolymerization is also included in the other monomers. These other monomers may be used alone or in combination of two or more.

The copolymerization reaction ratio of the above-mentioned diacetone acrylamide and a water-soluble monomer as another monomer is preferably 0.5 to 10 moles, more preferably 1.5 to 1 mole of the diacetone acrylamide. ~
The amount is 6.0 mol, particularly preferably 1.5 to 3.0 mol. This is because if the proportion of the water-soluble monomer exceeds 10 moles, the photosensitivity may decrease, while if it is less than 0.5 moles, the solubility may deteriorate, which is not preferable.

The water-soluble polymer thus obtained preferably has a weight average molecular weight of 10 × 10 ^{4 to} 100 × 10 ⁴ , and more preferably 20 × 10 ⁴ to 50.
It is × 10 ⁴ . The dispersity is 1 to 10, preferably 1 to 3, and more preferably 1 to 2.

When at least one selected from 4-azidobenzaldehyde-2-sulfonic acid and its salts is introduced into this water-soluble polymer by an aldol condensation reaction, the amount of introduction is diacetone acrylamide 100 from the viewpoint of photosensitivity. Most preferably, it is 5 to 95 mol%, more preferably 30 to 90 mol%, further preferably 50 to 90 mol%, and particularly preferably 80 to 90 mol% based on mol%.

Thus, a polymer compound (photopolymer) having a constitutional unit represented by the above general formula (I) can be obtained.

When vinyl acetate is used as the water-soluble monomer, diacetone acrylamide and vinyl acetate are copolymerized and an acetic acid group is hydrolyzed with an alkali to synthesize a hydroxyl group-containing water-soluble polymer. . This hydroxyl group-containing water-soluble polymer is preferably used because it becomes a water-soluble polymer capable of forming a pattern having extremely excellent water resistance by introducing an aldehyde by an acetalization reaction in an acidic aqueous solution.

Examples of such aldehydes include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and crotonaldehyde; aromatic aldehydes such as benzaldehyde, dialkylbenzaldehyde, alkylbenzaldehyde and cinnamicaldehyde. Aldehydes; heterocyclic aldehydes such as pyridine aldehyde and the like can be mentioned. These aldehydes also include 4-azidobenzaldehyde-2-sulfonic acid and salts thereof, formylstyrylpyridine and quaternized salts thereof, and the like. These aldehydes may be used alone or in combination of two or more. Practically preferably used are propionaldehyde, n-butyraldehyde,
Crotonaldehyde and the like, among which n-butyraldehyde is most preferably used.

In the acetalization reaction with the aldehydes, it is preferable that 15 mol% or less of all hydroxyl groups of the water-soluble polymer be acetalized. If it exceeds 15 mol%, it is difficult to obtain a water-soluble polymer having excellent stability.

The polymer compound (photopolymer) having the structural unit represented by the above general formula (I) has high sensitivity and
When exposed with a light amount of 0 mJ / cm ² , the gray scale method (Kodak Photographic Step) is used.
Table No. 2) can be used to expose 13 to 20 steps. It is possible to increase the sensitivity to 20 steps or more by appropriately selecting the ratio of the water-soluble monomer unit in the photopolymer and the amount of the azide compound introduced. However, in general, if the number exceeds 20 steps, the sensitivity will be too high. It is not preferable because the storage stability of the product is deteriorated and the handling becomes difficult.

In the present invention, in addition to the above essential constituents, a compatible polymer and various additives may be added, if necessary.
For example, a colorant, a plasticizer, a surfactant, a coupling agent for further improving the adhesion to the substrate, and the like can be appropriately added and mixed. In particular, by blending polyvinyl alcohol or modified polyvinyl alcohol as a compatible polymer, the releasability of the photoresist pattern can be improved. These polyvinyl alcohols and modified polyvinyl alcohols may be water-soluble ones and may be partially saponified or completely saponified. As the modified polyvinyl alcohol,
Diacetone acrylamide, acryloyl morpholine,
Various modified polyvinyl alcohols, such as those modified with N-vinyl-2-pyrrolidone and those with a silicone-containing group added to the side chain, can be used. These may be used alone or in combination of two or more.

In the water-soluble photosensitive resin composition of the present invention, the mixing ratio of the water-soluble polymer and the polymer compound (photopolymer) having the constitutional unit represented by the general formula (I) is 0.01 to 0.50. (Weight ratio) is preferable, and 0.05 to 0.20 is particularly preferable. This mixing ratio is 0.5
If it exceeds 0, the sensitivity is too high, and it becomes difficult to control the exposure. On the other hand, if it is less than 0.01, the sensitivity is insufficient and the practicality is lost.

Next, a method for forming a black matrix pattern according to the present invention using the water-soluble photosensitive resin composition of the present invention will be described.

According to the pattern forming method of the present invention, a photocurable pattern is formed using the above water-soluble photosensitive resin composition, a light absorbing substance is applied to the entire surface, dried, and then the photocurable pattern and the photocurable pattern are formed. A black matrix pattern is formed by peeling and removing the light absorbing material above.

First, the above water-soluble photosensitive resin composition is dissolved in water to a concentration of, for example, about 1 to 12% by weight and used as a coating solution, which is coated on a glass substrate. Since the water-soluble photosensitive resin composition of the present invention has high photocrosslinking efficiency, even if the coating amount is reduced so as to form a thin film having a photoresist layer thickness of about 0.1 to 0.5 μm, a pattern is formed during development after exposure. It is possible to form a photo-cured pattern without causing collapse or pattern flow. Therefore, the manufacturing cost can be reduced. The film thickness can be controlled by changing the number of rotations when, for example, a spinner coating method is used.

Next, the water-soluble photosensitive resin composition is applied and dried to expose the photoresist layer obtained through a shadow mask. The exposure is ultraviolet light, especially a wavelength of 300 to
A UV lamp that outputs light near 400 nm is preferably used, and the exposure amount thereof is slightly different depending on the composition of the water-soluble photosensitive resin composition, but is preferably about 1 to 10 mJ / cm ² . By using the water-soluble photosensitive resin composition of the present invention, it is possible to obtain a good photocuring pattern exhibiting reciprocity law failure characteristics in gap exposure. The reason for this is not clear, but it is thought to be roughly as follows.

That is, in the photo-curing reaction of the photoresist layer, the azide group contained in the photoresist layer is excited by exposure to generate nitrene, and the nitrenes or the nitrene and the polymer react with each other to crosslink,
It is said to cause photo-curing. However, in the presence of oxygen or water, this nitrene coexists with the above crosslinking reaction and the non-crosslinking reaction with oxygen or water, and as a result, the crosslinking reaction is suppressed. Polymers containing especially vinylpyrrolidone, eg polyvinylpyrrolidone (PVP)
Has excellent oxygen permeability, so in gap exposure,
Oxygen in the air is efficiently taken into the photoresist layer and reacts with the nitrene in the photoresist layer to suppress the above crosslinking reaction, so that a photocuring reaction occurs at the location corresponding to the central portion of the beam passage hole with high illuminance. On the other hand, the photo-curing reaction is suppressed at the portion corresponding to the peripheral portion of the low-illumination beam passage hole, and as a result, the through hole (beam passage hole) of the shadow mask
A photocured pattern of smaller dots is obtained. Therefore, the docking phenomenon unlike the conventional example does not occur. However, since the sensitivity of the entire photoresist layer is reduced accordingly, it is necessary to increase the illuminance in order to obtain a desired dot diameter. However, it has a structural unit represented by the above general formula (I) of the present invention. Since the polymer substance has high sensitivity, the crosslinking reaction proceeds efficiently even under low light conditions. Further, it is preferable to use a vinylpyrrolidone-vinylimidazole copolymer instead of polyvinylpyrrolidone because the sensitivity is further increased. Needless to say, when the water-soluble photosensitive resin composition of the present invention is used for contact exposure (exposure performed by bringing the mask into contact with the photoresist layer), a photocurable pattern faithful to the mask pattern can be formed.

Then, development is performed to remove the unexposed portion,
A photo-curing pattern is formed on a glass substrate. Development can be performed by a known method. In the present invention, even if the photoresist layer is formed of a thin film, pattern collapse and pattern flow at the time of development do not occur, and a good photocured pattern can be obtained.

Next, this is dried, and a liquid containing a light-absorbing substance is applied over the entire surface of the photo-curing pattern and the exposed substrate and dried again. Then, the photo-curing pattern is peeled and removed, and the photo-curing is performed. The light absorbing substance deposited on the pattern is also peeled off to form the black matrix pattern. The light absorbing substance is not particularly limited, and commonly used graphite is preferably used.
The above-mentioned peeling removal can be performed using a usual peeling agent or the like. Examples of the stripping agent include hypochlorites such as hypochlorous acid and sodium hypochlorite; hydrogen peroxide; peroxosulfates such as peroxosulfuric acid and potassium peroxosulfate;
In addition to periodate such as periodate and potassium periodate, an acidic aqueous solution such as permanganate and sulfamic acid is used. The water-soluble photosensitive resin composition of the present invention can be easily peeled by using these generally known peeling agents.

When the black matrix thus obtained is used for a color cathode ray tube, red is provided at a required black matrix hole or stripe portion.
Blue and green three primary color phosphors are filled, and an electron beam from an electron gun is passed through the through hole of a shadow mask to irradiate a desired phosphor on the panel to obtain a color image. By applying the water-soluble photosensitive resin composition and the method for forming a black matrix pattern of the present invention, a high-contrast and highly-clear color image can be obtained.

[0040]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited thereby.

I. Production of Water-Soluble Photosensitive Resin Composition [Production Example 1] 1-1. Combination of water-soluble polymer (base polymer) a solution
A flask was charged with 265 g of formed dimethyl acrylamide, 225 g of diacetone acrylamide, and 6.51 kg of pure water, and heated while bubbling with nitrogen gas.

When the temperature reached 65 ° C, the feeding of nitrogen gas was stopped, and 2,2'-azobis [2] was used as a polymerization initiator.
When 50 g of-(2'-imidazolin-2-yl) propane] dibasic acid ("VA-044"; manufactured by Wako Pure Chemical Industries, Ltd.) was added, the reaction solution was heated to 75 ° C, and this temperature was raised. The reaction was carried out for 2 hours while maintaining. Then room temperature (25
(.Degree. C.) and then heated to 70.degree. C. to precipitate the polymer. This polymer was separated by decantation and diluted with pure water to obtain 7.5 kg of a water-soluble polymer (base polymer) a solution having a solid content of 6% by weight. As a result of analysis, the average molecular weight of the polymer in this water-soluble polymer a solution was 25 × 10 ⁴ (DMF method, polystyrene standard).

1-2. Synthesis of Photopolymer a ′ Solution Base Polymer a Solution 1k Obtained in Synthesis Example 1-1 above
35 g of sodium 4-azidobenzaldehyde-2-sulfonate was dissolved in g, 20 ml of a 10% aqueous sodium hydroxide solution was added, and the reaction was carried out at room temperature (25 ° C.) for 6 hours. Then, it was neutralized with diluted hydrochloric acid and further diluted with pure water to obtain a photopolymer a'solution having a solid content of 2% by weight.

This photopolymer a'solution was spin-coated on a grained aluminum plate and dried to a film thickness of 0.5 μm.
m dry film was formed. The sensitivity of this was measured by the gray scale method. That is, a gray scale (Kodak Photographic Step) is formed on the film.
Table No. 2) was brought into close contact, exposed with an ultra-high pressure mercury lamp at an ultraviolet ray amount of 10 mJ / cm ² , and then developed by pouring pure water. After dyeing with an aqueous solution of methyl violet, washing with water and drying, photo-curing was performed up to 20 steps, and it was found that the photopolymer had good sensitivity.

1-3. Preparation of Sample A Polyvinylpyrrolidone (PVP) powder (K value = 90) was dissolved in pure water to prepare an aqueous solution having a concentration of 3% by weight. The above photopolymer a'solution was added to this, and the photopolymer a '/
The mixture was mixed so that PVP = 0.10 (weight ratio) and then diluted with pure water to prepare a sample A having a viscosity of 100 cP / 25 ° C.

[Evaluation of Sensitivity of Sample A] The same as the above except that Sample A was diluted with pure water to prepare a 2 wt% solids aqueous solution, and this was used instead of the photopolymer a ′ having 2 wt% solids. Then, the sensitivity was evaluated. As a result, it was found that up to 13 steps were photo-cured and the sensitivity was good.

[Manufacturing Example 2] 2-1. Combination of water-soluble polymer (base polymer) b solution
350 g of formed acryloylmorpholine, 140 g of diacetone acrylamide, and 5.51 kg of pure water were charged into a flask and heated while bubbling with nitrogen gas.

When the temperature reached 65 ° C, the feeding of nitrogen gas was stopped, and 2,2'-azobis [2] was used as a polymerization initiator.
When 50 g of-(2'-imidazolin-2-yl) propane] dibasic acid ("VA-044"; manufactured by Wako Pure Chemical Industries, Ltd.) was added, the reaction solution was heated to 75 ° C, and this temperature was raised. The reaction was carried out for 2 hours while maintaining. Then room temperature (25
(.Degree. C.) and then heated to 65.degree. C. to precipitate the polymer. This polymer was separated by decantation and diluted with pure water to obtain a water-soluble polymer (base polymer) b solution 6.5 having a solid content of 7.39% by weight.
kg. As a result of the analysis, the average molecular weight of the polymer in this water-soluble polymer b solution was 24 × 10 ⁴ (DMF method, based on polystyrene).

2-2. Synthesis of Photopolymer b ′ Solution Base polymer b solution 1k obtained in Synthesis Example 2-1 above
29 g of sodium 4-azidobenzaldehyde-2-sulfonate was dissolved in g, and 20 ml of a 10% aqueous sodium hydroxide solution was added, and the reaction was carried out at room temperature (25 ° C.) for 7 hours. Then, it was neutralized with dilute hydrochloric acid and further diluted with pure water to obtain a photopolymer b ′ solution having a solid content of 2% by weight.

When the sensitivity of the photopolymer b'solution was evaluated in the same manner as in Production Example 1, it was found that the photopolymer had good sensitivity up to 19 steps and had good sensitivity.

2-3. Preparation of Sample B Polyvinylpyrrolidone (PVP) powder (K value = 90) was dissolved in pure water to prepare an aqueous solution having a concentration of 3% by weight. The above photopolymer b'solution was added to this, and the photopolymer b '/
Mix so that PVP = 0.10 (weight ratio), then dilute this with pure water to obtain a sample B having a viscosity of 95 cP / 25 ° C.
Was prepared.

[Evaluation of Sensitivity of Sample B] Sensitivity evaluation was performed in the same manner as in Manufacturing Example 1 except that Sample A was replaced with Sample B. As a result, it was found that up to 12 steps were photo-cured and the sensitivity was good.

[Manufacturing Example 3] 3-1. Combined water-soluble polymer (base polymer) c solution
Forming acrylate 97 g, diacetone acrylamide 113
g, 2.79 kg of pure water into a flask to prepare an aqueous solution,
After further adding 25 g of sodium hydroxide, the mixture was heated while bubbling with nitrogen gas.

When the temperature reached 65 ° C, the feeding of nitrogen gas was stopped, and 2,2'-azobis [2] was used as a polymerization initiator.
When 15 g of-(2'-imidazolin-2-yl) propane] dibasic acid ("VA-044"; manufactured by Wako Pure Chemical Industries, Ltd.) was added, the reaction solution was heated to 72 ° C and then heated. The temperature was raised to 80 ° C., and the reaction was carried out for 1.5 hours while maintaining this temperature. Then, it was cooled to room temperature (25 ° C) and then heated to 65 ° C to precipitate a polymer. This polymer was separated by decantation and diluted with pure water to obtain a solid content of 8.30% by weight.
2.4 kg of water-soluble polymer (base polymer) c solution of
I got As a result of analysis, the average molecular weight of the polymer in this water-soluble polymer c solution was 20 × 10 ⁴ (DMF method, polystyrene standard).

3-2. Synthesis of Photopolymer c ′ Solution Base polymer c solution obtained in Synthesis Example 3-1 above.
Dissolve and add 15 g of sodium 4-azidobenzaldehyde-2-sulfonate to 3 kg, and further add pure water to add 5
It was an aqueous solution of 00 g. Next, 8 ml of 10% sodium hydroxide aqueous solution was added, and the reaction was carried out at room temperature (25 ° C.) for 8 hours. Then, it was neutralized with diluted hydrochloric acid and further diluted with pure water to obtain a photopolymer c ′ solution having a solid content of 2% by weight.

When the sensitivity of the photopolymer c ′ solution was evaluated in the same manner as in Production Example 1, it was found that the photopolymer was a photopolymer having good sensitivity after being photocured up to 16 steps.

3-3. Preparation of Sample C Polyvinylpyrrolidone (PVP) powder (K value = 90) was dissolved in pure water to prepare an aqueous solution having a concentration of 6% by weight. The above photopolymer c ′ solution was added to this, and the photopolymer c ′ /
The mixture was mixed so that PVP = 0.10 (weight ratio), and then this was diluted with pure water to prepare a sample C having a viscosity of 100 cP / 25 ° C.

[Evaluation of Sensitivity of Sample C] Sensitivity evaluation was carried out in the same manner as in Production Example 1 except that the sample A was replaced with the sample C. As a result, it was found that up to 13 steps were photo-cured and had good sensitivity.

[Manufacturing Example 4] 4-1. Combined water-soluble polymer (base polymer) d solution
Forming methacrylic acid 106 g, diacetone acrylamide 10
4 g and 2.79 kg of pure water were charged into a flask to make an aqueous solution, and 32 g of sodium hydroxide was further added, followed by heating while bubbling with nitrogen gas.

When the temperature reached 65 ° C, the feeding of nitrogen gas was stopped and 2,2'-azobis [2] was used as a polymerization initiator.
When 15 g of-(2'-imidazolin-2-yl) propane] dibasic acid ("VA-044"; manufactured by Wako Pure Chemical Industries, Ltd.) was added, the reaction solution was heated to 75 ° C and then heated. The temperature was raised to 80 ° C., and the reaction was carried out for 1.5 hours while maintaining this temperature. Then, it was cooled to room temperature (25 ° C) and then heated to 65 ° C to precipitate a polymer. This polymer was separated by decantation and diluted with pure water to obtain a solid content of 8.40% by weight.
2.4 kg of water-soluble polymer (base polymer) d solution of
I got As a result of analysis, the average molecular weight of the polymer in this water-soluble polymer d solution was 21 × 10 ⁴ (DMF method, polystyrene standard).

4-2. Synthesis of Photopolymer d'Solution Base polymer d solution obtained in Synthesis Example 4-1 above.
Dissolve and add 15 g of sodium 4-azidobenzaldehyde-2-sulfonate to 3 kg, and further add pure water to add 5
It was an aqueous solution of 00 g. Next, 8 ml of 10% sodium hydroxide aqueous solution was added, and the reaction was carried out at room temperature (25 ° C.) for 8 hours. Then, it was neutralized with diluted hydrochloric acid and further diluted with pure water to obtain a photopolymer d ′ solution having a solid content of 2% by weight.

When the sensitivity of the photopolymer d ′ solution was evaluated in the same manner as in Production Example 1, it was found that the photopolymer was photocured up to 16 steps and had good sensitivity.

4-3. Preparation of Sample D Polyvinylpyrrolidone (PVP) powder (K value = 90) was dissolved in pure water to prepare an aqueous solution having a concentration of 6% by weight. The above photopolymer d'solution was added to this, and the photopolymer d '/
The mixture was mixed so that PVP = 0.10 (weight ratio), and then this was diluted with pure water to prepare a sample D having a viscosity of 100 cP / 25 ° C.

[Evaluation of Sensitivity of Sample D] Sensitivity evaluation was performed in the same manner as in Production Example 1 except that Sample A was replaced with Sample D. As a result, it was found that up to 13 steps were photo-cured and had good sensitivity.

[Manufacturing Comparative Example 1] Preparation of Comparative Sample X Polyvinylpyrrolidone (PVP) powder (K value = 90) was dissolved in pure water to prepare an aqueous solution having a concentration of 3% by weight. 4,4'-diazidostilbene-2,2'-disulfonic acid disodium was added thereto, and 4,4'-diazidostilbene-2,2'-disulfonic acid disodium / PVP = 0.
10 (weight ratio) was mixed, and this was then diluted with pure water to prepare a comparative sample X having a viscosity of 95 cP / 25 ° C.

[Evaluation of Sensitivity of Comparative Sample X] Comparative sample X was diluted with pure water to prepare an aqueous solution having a solid content of 3% by weight, spin-coated on an aluminum substrate and dried to form a dry film having a thickness of 1.0 μm. did. The sensitivity of this was measured by the gray scale method described in Manufacturing Example 1. As a result, it was found that photo-curing was performed only up to 8 steps and that the sensitivity was lower than that of the samples A to D.

Manufacturing Example 5 Polyvinylpyrrolidone (PVP) powder (K value = 90) was dissolved in pure water to prepare an aqueous solution having a concentration of 3% by weight. In addition to the above manufacturing example 1
-2, the photopolymer a'solution obtained in -2 was mixed so that the photopolymer a '/ PVP = 0.03 (weight ratio), and then diluted with pure water to obtain a viscosity of 100 cP / 25.
Sample E at 0 ° C was prepared.

[Evaluation of Sensitivity of Sample E] The sensitivity was evaluated in the same manner as in Manufacturing Example 1 except that the sample A was replaced with the sample E. As a result, it was found that up to 9 steps were photo-cured and the sensitivity was good.

[Production Example 6] Polyvinylpyrrolidone (PVP) powder (K value = 90) was dissolved in pure water to prepare an aqueous solution having a concentration of 3% by weight. In addition to the above manufacturing example 1
-2, the photopolymer a'solution obtained in -2 was mixed so that the photopolymer a '/ PVP = 0.20 (weight ratio), and then diluted with pure water to obtain a viscosity of 100 cP / 25.
Sample F at 0 ° C was prepared.

[Evaluation of Sensitivity of Sample F] Sensitivity evaluation was performed in the same manner as in Manufacturing Example 1 except that Sample A was replaced with Sample F. As a result, it was found that up to 14 steps were photo-cured and had good sensitivity.

[Production Example 7] Polyvinylpyrrolidone (PVP) powder (K value = 90) was dissolved in pure water to prepare an aqueous solution having a concentration of 3% by weight. In addition to the above manufacturing example 1
-2, the photopolymer a'solution obtained in -2 was mixed so that the photopolymer a '/ PVP = 0.40 (weight ratio), and then diluted with pure water to obtain a viscosity of 100 cP / 25.
Sample G at 0 ° C was prepared.

[Sensitivity Evaluation of Sample G] The sensitivity evaluation was performed in the same manner as in Manufacturing Example 1 except that the sample A was replaced with the sample G. As a result, it was found that up to 18 steps were photo-cured and had good sensitivity.

[Production Example 8] Polyvinylpyrrolidone (PVP) powder (K value = 60) was dissolved in pure water to prepare an aqueous solution having a concentration of 6.5% by weight. This was mixed with the photopolymer a'solution obtained in Production Example 1-2 described above so that the photopolymer a '/ PVP = 0.10 (weight ratio), and this was diluted with pure water to give a viscosity of 100 cP. / 2
Sample H at 5 ° C was prepared.

[Evaluation of Sensitivity of Sample H] The above sample H was diluted with pure water to prepare an aqueous solution having a solid content of 3% by weight, spin-coated on an aluminum substrate and dried to form a dry film having a thickness of 0.8 μm. . The sensitivity of this was measured by the gray scale method described in Manufacturing Example 1. As a result, it was found that up to 10 steps were photo-cured and the sensitivity was good.

[Manufacturing Example 9] 9-1. Combination of water-soluble polymer (base polymer) e solution
86g formed methacrylic acid, the charged amount of diacetone acrylamide, respectively, except that in place of 114 g, prepared in Example 4
A water-soluble polymer (base polymer) e solution having a solid content of 5.00% by weight was obtained in the same manner as in. As a result of the analysis, the average molecular weight of the polymer in this water-soluble polymer e solution was 25 ×
10 ⁴ (DMF method, based on polystyrene), and the content of diacetone acrylamide was 40 mol%.

9-2. Synthesis of Photopolymer e ′ Solution Base polymer e solution obtained in Synthesis Example 9-1 above.
4 g of sodium 4-azidobenzaldehyde-2-sulfonate was dissolved and added to 1 kg, and then 2 ml of a 10% sodium hydroxide aqueous solution was added, and the reaction was carried out at room temperature (25 ° C.) for 7 hours. Then, it was neutralized with dilute hydrochloric acid and further diluted with pure water to obtain a photopolymer e ′ solution having a solid content of 7% by weight.

This photopolymer e ′ solution was spin-coated on a grained aluminum plate and dried to give a film thickness of 0.5 μm.
m dry film was formed. The sensitivity of this was measured by the gray scale method. That is, a gray scale (Kodak Photographic Step) is formed on the film.
Table No. 2) was brought into close contact, exposed with an ultra-high pressure mercury lamp at an ultraviolet ray amount of 10 mJ / cm ² , and then developed by pouring pure water. After dyeing with a methyl violet aqueous solution, washing with water and drying, photo-curing was performed up to 18 steps, and it was found that the photopolymer had good sensitivity.

9-3. Preparation of Sample I Vinylpyrrolidone-Vinylimidazole (VP-VI)
Copolymer powder [K value = 90, VP: VI = 90: 10]
(Mole% ratio)] 7 g was dissolved in 100 g of pure water. 10 g of the above-mentioned photopolymer e ′ solution was added and dissolved therein to prepare a sample I of photopolymer e ′ / VP-VI = 0.10 (weight ratio).

[Sensitivity Evaluation of Sample I] The sensitivity evaluation was performed in the same manner as in Manufacturing Example 1 except that the sample A was replaced with the sample I. As a result, it was found that up to 15 steps were photo-cured and the sensitivity was good.

[Manufacturing Example 10] Manufacturing Example 9 except that the VP-VI copolymer was replaced with PVP (K value = 90).
Sample J was prepared in the same manner as in.

[Evaluation of Sensitivity of Sample J] The sensitivity was evaluated in the same manner as in Manufacturing Example 1 except that Sample J was used instead of Sample A. As a result, it was found that up to 13 steps were photo-cured and had good sensitivity.

[Production Comparative Example 2] Production process except that the photopolymer e'solution was replaced with disodium 4,4'-diazidostilbene-2,2'-disulfonate and the addition amount was changed from 10 g to 0.7 g. Comparative sample Y was prepared in the same manner as in Example 9.

[Evaluation of Sensitivity of Comparative Sample Y] Sensitivity evaluation was performed in the same manner as in Manufacturing Example 1 except that the sample A was replaced with the comparative sample Y. As a result, the photo-curing was performed only up to 8 steps.

[Manufacturing Comparative Example 3] A comparative sample Z was prepared in the same manner as in Manufacturing Comparative Example 2 except that PVP (K value = 90) was used in place of the VP-VI copolymer.

[Evaluation of Sensitivity of Comparative Sample Z] Sensitivity evaluation was performed in the same manner as in Manufacturing Example 1 except that the sample A was replaced with the comparative sample Z. As a result, the photo-curing reaction does not proceed sufficiently,
The pattern leaked during development.

[Manufacturing Example 11] Sample K was prepared in the same manner as in Manufacturing Example 9 except that K value = 80 and VP: VI = 80: 20 (mole% ratio) were used instead of the VP-VI copolymer. .

[Evaluation of Sensitivity of Sample K] Sensitivity evaluation was performed in the same manner as in Manufacturing Example 1 except that Sample A was replaced with Sample K. As a result, it was found that up to 12 steps were photo-cured and had good sensitivity.

[Manufacturing Example 12] Sample L was prepared in the same manner as in Manufacturing Example 9 except that K value = 60 and VP: VI = 75: 25 (mole% ratio) were used instead of the VP-VI copolymer. .

[Evaluation of Sensitivity of Sample L] The sensitivity was evaluated in the same manner as in Manufacturing Example 1 except that the sample A was replaced with the sample L. As a result, it was found that up to 10 steps were photo-cured and the sensitivity was good.

II. Formation of Black Matrix Pattern [Example 1] Sample A50 obtained in the above Production Example 1
g, pure water 50 g, nonionic surfactant (“LT-22
1 ”; 1 g of a 10% aqueous solution of NOF CORPORATION was mixed to prepare a coating solution.

A washed glass plate (125 mm) was used as a substrate, and a coating solution having the above composition was applied to the substrate 1 times.
It was spin-coated at 20 rpm and dried at 50 ° C. for 15 minutes to form a photoresist layer (film thickness 1.0 μm).

A gap of 10 m is formed on the photoresist layer.
at a light intensity of 0.15 mW / cm ² with an ultra-high pressure mercury lamp that outputs light with a wavelength of around 350 nm through a shadow mask having a through hole of a predetermined dot pattern at 1 m.
Point light source exposure was performed at intervals of 0, 20, 30, and 40 seconds.

After the exposure, the film was developed with water to remove the unexposed portion and then dried with hot air at 50 ° C. for 10 minutes to obtain a photo-cured pattern.

Graphite slurry (“GA-66S”; manufactured by Hitachi Powdered Metals Co., Ltd.) was spun at 150 rpm on the glass substrate on which the photo-cured pattern was formed and over the entire surface of the photo-cured pattern and the exposed substrate. Spin coating, and dried at 50 ° C. for 15 minutes.

Next, this was immersed in a 15% hydrogen peroxide aqueous solution at 50 ° C. for 1 minute and then rinsed with water having a pressure of 4 kg / cm ² to find that there was little fringe and holes were formed at positions corresponding to the through holes of the shadow mask. To obtain a black matrix pattern. The results of measuring the dimensions of the black matrix holes are shown in FIG. 1 and Table 1.

In FIG. 1 and Table 1, the black matrix hole diameter is based on the hole dimension diameter (diameter) when water development is performed after exposure for 20 seconds using the comparative sample X as a reference (1.00). , The relative value is shown.

Example 2 50 g of the sample B obtained in the above Production Example 2, 50 g of pure water, and 1 g of a 10% aqueous solution of a nonionic surfactant (“LT-221” manufactured by NOF CORPORATION) were mixed. Then, a coating liquid was prepared.

Using this coating solution, a black matrix pattern was formed in the same manner as in Example 1 above. As a result, a black matrix pattern having few fringes and having holes formed at positions corresponding to the through holes of the shadow mask was formed. Obtained. The results of measuring the dimensions of the black matrix holes are shown in FIG. 1 and Table 1.

Comparative Example 1 50 g of the comparative sample X obtained in the above Production Comparative Example 1, 50 g of pure water, and 1 g of a 10% aqueous solution of a nonionic surfactant (“LT-221”; manufactured by NOF CORPORATION). By mixing, a coating solution was prepared.

Using this coating solution, a black matrix pattern was formed in the same manner as in Example 1 above, and the same black matrix pattern with less fringes as in Examples 1 and 2 was obtained. The results of measuring the dimensions of the black matrix holes are shown in FIG. 1 and Table 1.

In Examples 1 and 2 and Comparative Example 1 above, as is clear from the relationship between the exposure time and the dimensional change of the black matrix hole diameter shown in FIG. 1 and Table 1, when Comparative Sample X was used, Even if long-time exposure is performed, the portion where the light irradiation intensity is small (the peripheral portion of the light passage hole of the mask) is not photocured. Therefore, in order to obtain a desired pattern dimension (for example, 1.00). It turns out that it is necessary to irradiate light of relatively high intensity. On the other hand, in the case of using the samples A and B, the cross-linking reaction is efficiently progressing even in the portion where the irradiation intensity of light is small, so that the pattern formation can be performed even with a low exposure amount. Also, a sufficient hole diameter can be obtained with an exposure time of 1/2 or less compared with the comparative sample X.

Example 3 50 g of the sample C obtained in the above Production Example 3, 50 g of pure water, and 1 g of a 10% aqueous solution of a nonionic surfactant (“LT-221”; manufactured by NOF CORPORATION) were mixed. Then, a coating liquid was prepared.

Using this coating solution, a black matrix pattern was formed in the same manner as in Example 1 above. As a result, a black matrix pattern having few fringes and having holes formed at positions corresponding to the through holes of the shadow mask was formed. Obtained. The results of measuring the dimensions of the black matrix holes are shown in Table 1.

Example 4 50 g of the sample D obtained in the above Production Example 4, 50 g of pure water, and 1 g of a 10% aqueous solution of a nonionic surfactant (“LT-221”; manufactured by NOF CORPORATION) were mixed. Then, a coating liquid was prepared.

Using this coating solution, a black matrix pattern was formed in the same manner as in Example 1. As a result, a black matrix pattern having few fringes and having holes formed at positions corresponding to the through holes of the shadow mask was formed. Obtained. The results of measuring the dimensions of the black matrix holes are shown in Table 1.

Example 5 50 g of the sample E obtained in the above Production Example 5, 50 g of pure water, and 1 g of a 10% aqueous solution of a nonionic surfactant (“LT-221”; manufactured by NOF CORPORATION) were mixed. Then, a coating liquid was prepared.

Using this coating solution, a black matrix pattern was formed in the same manner as in Example 1. As a result, a black matrix pattern having few fringes and having holes formed at positions corresponding to the through holes of the shadow mask was formed. Obtained. The results of measuring the dimensions of the black matrix holes are shown in Table 1.

Example 6 50 g of the sample F obtained in the above Production Example 6, 50 g of pure water, and 1 g of a 10% aqueous solution of a nonionic surfactant (“LT-221”; manufactured by NOF CORPORATION) were mixed. Then, a coating liquid was prepared.

Using this coating solution, a black matrix pattern was formed in the same manner as in Example 1. As a result, a black matrix pattern having few fringes and having holes formed at positions corresponding to the through holes of the shadow mask was formed. Obtained. The results of measuring the dimensions of the black matrix holes are shown in Table 1.

Example 7 50 g of the sample G obtained in the above Production Example 7, 50 g of pure water, and 1 g of a 10% aqueous solution of a nonionic surfactant (“LT-221”; manufactured by NOF CORPORATION) were mixed. Then, a coating liquid was prepared.

Using this coating solution, a black matrix pattern was formed in the same manner as in Example 1. As a result, a black matrix pattern having few fringes and having holes formed at positions corresponding to the through holes of the shadow mask was formed. Obtained. The results of measuring the dimensions of the black matrix holes are shown in Table 1.

Example 8 50 g of the sample H obtained in Production Example 8 above, 50 g of pure water, and 1 g of a 10% aqueous solution of a nonionic surfactant (“LT-221”; manufactured by NOF CORPORATION) were mixed. Then, a coating liquid was prepared.

Using this coating solution, a black matrix pattern was formed in the same manner as in Example 1 above. As a result, a black matrix pattern having few fringes and having holes formed at positions corresponding to the through holes of the shadow mask was formed. Obtained. The results of measuring the dimensions of the black matrix holes are shown in Table 1.

Example 9 A black matrix pattern was formed in the same manner as in Example 1 except that the thickness of the photoresist layer was changed to 0.5 μm in Example 1 above. As a result, as shown in Table 1, exposure time 1
A hole having a hole diameter of 1.05 was formed at 0 seconds, and a good pattern could be formed even by short-time exposure.

Comparative Example 2 Exposure and development were performed in the same manner as in Comparative Example 1 except that the thickness of the photoresist layer in Comparative Example 1 was changed to 0.5 μm. as a result,
As shown in Table 1, at any of the exposure times of 10, 20, and 30 seconds, the pattern flowed off during water development. If the exposure time is 40 seconds, the hole diameter is 0.51
However, there were many fringes and the shape was poor.

[0116]

[Table 1] As is clear from Table 1, the water-soluble photosensitive resin compositions of the present invention shown in Examples 1 to 9 can obtain a desired sufficient black matrix hole diameter even when exposed for a short time and at a low exposure amount. It can be seen that the photo-curing pattern can be efficiently formed even with a thin film.

[Example 10] 50 g of the sample I obtained in the above Production Example 9, 50 g of pure water, and 10% of the silane coupling agent ("KBM603": manufactured by Shin-Etsu Silicon Co., Ltd.)
1 ml of ethanol solution, nonionic surfactant (“LT
-221 "; 1 ml of 10% aqueous solution of NOF CORPORATION
Were mixed to prepare a coating liquid.

A washed glass plate (125 mm) was used as a substrate, and a coating solution having the above composition was applied to the substrate 1 times.
It was spin-coated at 20 rpm and dried at 50 ° C. for 15 minutes to form a photoresist layer (film thickness 1.0 μm).

A gap of 10 m is formed on the photoresist layer.
at a light intensity of 0.10 mW / cm ² with an ultra-high pressure mercury lamp that outputs light with a wavelength of about 350 nm through a shadow mask having a through hole of a predetermined dot pattern at 25 m.
Point light source exposure was performed for a second.

After the exposure, the water phenomenon was performed to remove the unexposed portion, and then it was dried with hot air at 50 ° C. for 10 minutes to obtain a photo-cured pattern.

On the glass substrate on which the photo-cured pattern was formed, graphite slurry (“Hitasol GA-66M”; manufactured by Hitachi Powdered Metals Co., Ltd.) 2 was spread over the entire surface of the photo-cured pattern and the exposed substrate. Double dilution (diluted with water)
Was spin-coated at 150 rpm and dried at 50 ° C. for 15 minutes.

Then, this was immersed in a saturated sulfamic acid aqueous solution at 25 ° C. for 1 minute and then rinsed with water having a pressure of 3 kg / cm ² to find that there were no fringes and holes were formed at the positions corresponding to the through holes of the shadow mask. The obtained black matrix pattern was obtained. Table 2 shows the results of measuring the dimensions of the black matrix holes and the evaluation of the releasability of the photoresist.

In Table 2, the black matrix hole diameter is the same as that of Comparative Sample Z obtained in Production Comparative Example 3 above.
Is used as a reference (1.00) for the hole size diameter (diameter) when water development is performed after exposure for 25 seconds.

Further, the peeling property was evaluated as follows. [Releasability] After applying the phosphor slurry, washing, removing, and drying it in an undried state, the presence or absence of light emission by the residual phosphor in the hole with a black light that emits ultraviolet rays in the phosphor emission wavelength range, and visual inspection The peeling residue of the photoresist layer was examined. (Evaluation) ◎: No peeling residue ○: Very thin peeling residue. No adherence of phosphor X: Somewhat deep peeling residue remains. Some parts have fluorescent material attached.

Example 11 A coating liquid was prepared in the same manner as in Example 10 except that the sample J obtained in Production Example 10 was used.

Using this coating solution, a black matrix pattern was formed in the same manner as in Example 10. As a result, a black matrix pattern having no fringes and having holes formed at positions corresponding to the through holes of the shadow mask was formed. Obtained. Table 2 shows the results of measuring the dimensions of the black matrix holes and the evaluation of the releasability of the photoresist.

[Comparative Example 3] A coating solution was prepared in the same manner as in Example 10 except that the comparative sample Y obtained in Production Comparative Example 2 was used.

When a black matrix pattern was formed using this coating solution in the same manner as in Example 10, a black matrix pattern having no fringes and having holes formed at positions corresponding to the through holes of the shadow mask was formed. Obtained. Table 2 shows the results of measuring the dimensions of the black matrix holes and the evaluation of the releasability of the photoresist.

[Comparative Example 4] A coating solution was prepared in the same manner as in Example 10 except that Comparative Sample Z obtained in Production Comparative Example 3 was used.

Using this coating solution, a black matrix pattern was formed in the same manner as in Example 10. As a result, a black matrix pattern having no fringes and having holes formed at positions corresponding to the through holes of the shadow mask was formed. Obtained. Table 2 shows the results of measuring the dimensions of the black matrix holes and the evaluation of the releasability of the photoresist.

[Example 12] A coating solution was prepared in the same manner as in Example 10 except that the sample K obtained in Production Example 11 was used.

When a black matrix pattern was formed using this coating solution in the same manner as in Example 10, a black matrix pattern having no fringes and having holes formed at positions corresponding to the through holes of the shadow mask was formed. Obtained. Table 2 shows the results of measuring the dimensions of the black matrix holes and the evaluation of the releasability of the photoresist.

[Example 13] A coating solution was prepared in the same manner as in Example 10 except that the sample L obtained in Production Example 12 was used.

When a black matrix pattern was formed using this coating solution in the same manner as in Example 10, a black matrix pattern having no fringes and having holes formed at positions corresponding to the through holes of the shadow mask was formed. Obtained. Table 2 shows the results of measuring the dimensions of the black matrix holes and the evaluation of the releasability of the photoresist.

[Example 14] A pattern was formed in the same manner as in Example 10 except that the film thickness was changed to 0.5 µm. As a result, no fringes were formed and holes were formed at positions corresponding to the through holes of the shadow mask. The obtained black matrix pattern was obtained. Table 2 shows the results of measuring the dimensions of the black matrix holes and the evaluation of the releasability of the photoresist.

[0136]

[Table 2]

[0137]

As described above in detail, the water-soluble photosensitive resin composition of the present invention can efficiently form a photo-curing pattern even with a thin film, so that reduction in material cost can be expected. Further, since the sensitivity is high, a pattern can be formed in a short time with a small exposure amount, and the throughput is improved. Further, since the peeling property is good and almost no peeling residue occurs, it is possible to prevent color mixture due to adhesion of the phosphor.
Therefore, it is possible to reduce the manufacturing cost, improve the manufacturing efficiency, and manufacture high-quality products. Further, even in the case of the gap exposure, the docking phenomenon does not occur, and a good photo-curing pattern can be obtained in both the contact exposure and the gap exposure, and it can be applied in a wide range. Therefore, by producing a black matrix using the water-soluble photosensitive resin composition of the present invention, it is possible to obtain a clear color image with high sensitivity and high resolution.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the exposure time and the black matrix hole diameter of Samples A and B and Comparative Sample X used in Examples.

Claims (8)

[Claims] 1. A compound represented by the following general formula (I) In the water-soluble photosensitive resin composition comprising a polymer compound having a structural unit represented by the formula (wherein X represents Na, K or NH ₄ ) and a water-soluble polymer, the water-soluble polymer is polyvinyl. A water-soluble photosensitive resin composition, which is at least one selected from the group consisting of pyrrolidone and a copolymer of vinylpyrrolidone and vinylimidazole. 2. The copolymer is vinylpyrrolidone:
Vinylimidazole = 95: 5-10: 90 (mol%
The water-soluble photosensitive resin composition according to claim 1, which is a copolymer of 3. The copolymer is vinylpyrrolidone:
Vinylimidazole = 95: 5 to 50:50 (mol%
The water-soluble photosensitive resin composition according to claim 1, which is a copolymer of 4. The copolymer is vinylpyrrolidone:
Vinyl imidazole = 90:10 to 75:25 (mol%
The water-soluble photosensitive resin composition according to claim 1, which is a copolymer of 5. The water-soluble polymer has the following formula 1 (Wherein C represents the number of grams of the polymer contained in 100 ml of the water-soluble polymer aqueous solution; η _r represents the relative viscosity of the polymer), and the K value satisfying the relational expression is 30.
The water-soluble photosensitive resin composition according to any one of claims 1 to 4, which is -100. 6. The water-soluble photosensitive resin composition according to claim 5, wherein the K value is 50 to 100. 7. The K value is 60-95.
The water-soluble photosensitive resin composition described in 1. 8. A photocurable pattern is formed on a substrate using the water-soluble photosensitive resin composition according to claim 1, and then a light-absorbing substance is applied to the entire surface and dried, A method for forming a black matrix pattern, which comprises forming a black matrix pattern by peeling and removing the light-curable pattern and the light-absorbing substance thereon.