JPH11160865A - Water-soluble photosensitive composition and forming method of black matrix pattern by using that - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-soluble photosensitive compsn. which has high sensitivity and excellent adhesion property with a glass substrate, which is easily peeled with little residue of peeling, and which has a long life and excellent storage stability, as a photoresist especially to be used for the production of a black matrix of a color CRT or the like. SOLUTION: This water-soluble photosensitive compsn. is prepared by compounding a photosensitive bis azide compd. and a water-soluble polymer comprising two kinds of compds. of polyvinylalcohol and vinyl pyrrolidone- vinylimidazole copolymer. After a pattern is formed on a substrate by hardening the water-soluble photosensitive compsn. above described with light, a light- absorbing material is applied all over the substrate and dried. Then the photoset pattern and the light-absorbing material on the pattern are removed by peeling to form a black matrix pattern on the substrate.

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 composition 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. A water-soluble photosensitive composition that is highly sensitive, has excellent adhesion to a glass substrate, can be easily peeled off, has no peeling residue, has a long service life, and has excellent storage stability, and black using the same. The present invention relates to a method for forming a matrix pattern.

[0002]

2. Description of the Related Art A black matrix used for a fluorescent screen of a color CRT such as a color television is usually formed by forming a black matrix made of a light-absorbing substance (eg, graphite) on a glass panel in a predetermined pattern.
The portion other than the pattern portion forms many small holes (black matrix holes) or stripes (black stripes). Usually, red (R), green (G), and blue (B) three primary color phosphors are filled in the black matrix holes or stripes to form three primary color phosphor dots (patterns).
An electron beam is emitted from an electron gun, the beam is passed through a number of through holes formed in a shadow mask, and the phosphor dots are selectively stimulated to emit light, thereby forming a color image on a 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.
When the positional correspondence is shifted, the electron beam does not hit the target phosphor, or hits another phosphor, and the color reproducibility decreases. Therefore, in forming a pattern of the black matrix, it is necessary to form a black matrix hole or a stripe portion on the inner surface of the glass panel while maintaining a positional relationship exactly corresponding to the through hole of the shadow mask. for that reason,
In general, as an exposure mask used when forming a black matrix pattern, a shadow mask itself used for a color CRT is used.

Usually, in forming such a black matrix pattern, first, a water-soluble photosensitive composition is applied on a glass substrate to form a photoresist layer, and the exposed portion of the photoresist layer is exposed to light through a shadow mask. After curing and developing to remove the unexposed portions to form a photo-cured pattern, apply a light-absorbing substance over the entire surface of the photo-cured pattern and the exposed substrate, and dry to form a black film. . Next, the photo-cured pattern is peeled off and the black film on the photo-cured pattern is also peeled off 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, by filling each of the three primary color phosphors of red (R), green (G), and blue (B) into the matrix holes or the stripes to form a three primary color phosphor pattern, the phosphor screen is formed. Has been produced.

As a water-soluble photosensitive composition used for forming such a black matrix pattern, conventionally,
A polyvinyl alcohol-bichromate type, a water-soluble polymer-water-soluble bisazide compound type, and the like are used.

However, in the case of the polyvinyl alcohol-bichromate system, the change in sensitivity increases with time,
In addition, there is a problem that the resolution is poor and the cross-linking area is increased due to a dark reaction after stopping the exposure. Therefore, if exposure, development, and filling are performed three times in order to sequentially form the three primary color phosphor patterns, light irradiated to the photoresist layer will overlap between the patterns, and should be separated if they should be. There is a problem that a phenomenon called so-called docking is likely to occur, in which adjacent phosphor patterns of other colors continue. Such a problem has been a serious problem particularly in gap exposure in which exposure is performed by separating the mask without contacting the photoresist layer. To avoid this docking phenomenon,
For example, JP-A-48-79970 discloses a method using polyvinylpyrrolidone as a water-soluble polymer of a water-soluble polymer-water-soluble bisazide compound-based water-soluble photosensitive composition. That is, when polyvinylpyrrolidone is used, when the integrated value of light irradiation is less than a certain value, the resulting crosslinking hardly progresses (“reciprocity failure property”). Is relatively steep at a location relatively close to the center of the beam passage hole, and the degree of cross-linking decreases significantly 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 necessary for forming dots, and the diameter of the resulting dot is smaller than the diameter of the beam passage hole, and docking does not occur. . However, Japanese Patent Laid-Open No.
The water-soluble polymer-water-soluble bisazide compound system disclosed in JP-A-79970 has excellent resolution but low sensitivity and poor adhesion to a glass substrate. It is necessary to add a certain amount or more of an adhesiveness improving agent such as an agent. However, silane coupling agents are liable to decompose and degrade in water, causing the adhesive strength to the glass substrate to change over time and the formation of foreign matter in the coating solution, and the storage stability of the coating solution to be poor. It has the disadvantage that the life is extremely short. In addition, the photoresist layer is not completely removed at the time of peeling, so that a peeling residue occurs. Therefore, in the next step of forming the phosphor, the phosphor adheres to the peeling residue, causing a problem of causing color mixing.

Therefore, the present applicant has developed a water-soluble photosensitive composition having good adhesion to a glass substrate even when the amount of the silane coupling agent used is reduced (Japanese Patent Laid-Open No. 9-12015).
No. 9). This uses a vinyl pyrrolidone-vinyl imidazole copolymer (VP-VI copolymer) as a water-soluble non-photosensitive polymer. The present invention relates to a further improved water-soluble photosensitive composition obtained by further improving this water-soluble photosensitive composition.

[0008]

DISCLOSURE OF THE INVENTION The present invention is particularly applicable to a photoresist used for producing a black matrix such as a color cathode ray tube, which has high sensitivity, excellent adhesion to a glass substrate, can be easily peeled, and has a peeling residue. Not
An object of the present invention is to provide a water-soluble photosensitive composition having a long service life and excellent storage stability, and a method for forming a black matrix pattern using the composition.

[0009]

Means for Solving the Problems The present inventors have proposed the use of two specific polymers as water-soluble polymers in a water-soluble polymer-photosensitive bisazide compound-based water-soluble photosensitive composition. The inventors have found that the above-mentioned problems can be solved, and have completed the present invention based on the findings.

That is, the present invention comprises (A) (a) a vinylpyrrolidone-vinylimidazole copolymer, and (b) a water-soluble polymer comprising two kinds of polymers, polyvinyl alcohol, and (B) a photosensitive bisazide compound. And a water-soluble photosensitive composition.

Further, the present invention provides a method of forming a photo-curing pattern on a substrate using the above water-soluble photosensitive composition, applying a light-absorbing substance over the whole surface, drying the photo-curing pattern and drying the photo-curing pattern and the light on the photo-curing pattern. The present invention relates to a method of forming a black matrix pattern on a substrate by peeling and removing an absorbent material.

[0012]

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

The water-soluble polymer as the component (A) is
It consists of two polymers, (a) vinylpyrrolidone-vinylimidazole copolymer and (b) polyvinyl alcohol.

(A) The vinylpyrrolidone-vinylimidazole copolymer (VP-VI copolymer) includes K
Those having a value of 60 to 100 are preferred, and especially 85 to 95.
It is. Here, the K value is a value that depends on the molecular weight,
Equation 1 below

[0015]

(Equation 1)

[0016] (wherein, C is vinylpyrrolidone - vinylimidazole copolymer solution the vinyl pyrrolidone contained in the 100 ml - indicates the number of grams of vinylimidazole copolymer; - indicates the relative viscosity of vinylimidazole copolymers eta _r is the vinyl pyrrolidone) in It satisfies the relational expression represented. In the above formula, the relative viscosity (η _r ) refers to the specific viscosity of the solution with respect to the solvent, and a solution having a certain concentration (here, the vinylpyrrolidone-
Assuming that the viscosity of a solution of 1 g of vinylimidazole copolymer in 100 ml of water) is η and the viscosity of the solvent is η _o , the relative viscosity (η _r ) is determined by η _r = η / η _o . If the K value is too high, the viscosity becomes high, it is difficult to control the photoresist film thickness, and the releasability tends to decrease. On the other hand, if the K value is too low, the photocurability decreases,
It becomes difficult to form a desired photocurable pattern.

Further, vinylpyrrolidone (VP): vinylimidazole (VI) = 99.99: 0.01 to 98:
2 (mole% ratio) is preferred, and especially 99.
A ratio of about 9: 0.1 to 99: 1 (molar%) is preferred. When the ratio of VI to VP is smaller than the above range, the effect of improving the adhesiveness to the glass substrate is not sufficiently exhibited. On the other hand, when the ratio exceeds the above range, scum tends to be generated at the time of peeling, and the resolution tends to deteriorate. Is not preferred.

(B) The polyvinyl alcohol (PVA) preferably has a degree of saponification of 80 to 95 mol%, particularly preferably 85 to 90 mol%. In addition, the degree of polymerization is 3
Those having about 00 to 1800 are preferable, and especially 800 to 1800.
About 1200 is preferable. If the degree of saponification is out of the above range, the applicability to the substrate tends to decrease, and if the degree of polymerization is out of the above range, the resolution tends to decrease, which is not preferable.

In the present invention, the above-mentioned "vinylpyrrolidone" means N-vinyl-2-pyrrolidone, and "vinylimidazole" means all of N-vinyl, 2-vinyl, 4-vinyl and the like. And isomers of

By blending the two components (a) and (b) as the component (A), the adhesiveness and peelability of the water-soluble photosensitive composition of the present invention to a glass substrate can be improved. In addition, this eliminates the need for using a silane coupling agent, and can improve the service life and storage stability of the coating solution.

(A) In a water-soluble polymer, (a) V
The mixing ratio of the P-VI copolymer and (b) PVA is VP
-VI copolymer: PVA = 95: 5 to 30:70 (weight ratio) is preferred, more preferably 90:10 to 4
It is about 0:60 (weight ratio). If the compounding ratio of the component (a) is less than the above range, the effect of improving the adhesiveness to the glass substrate is not sufficient, while if it exceeds the above range, sensitivity, resolution,
The tendency of the peelability of the photocurable pattern to decrease is increased, which is not preferable.

The sensitivity is increased by increasing the amount of the component (b), but when the component (b) is added beyond the above range, the sensitivity is lowered and the resolution is also deteriorated. There is a tendency.

As the photosensitive bisazide compound as the component (B), for example, the following general formula (I)

[0024]

Embedded image

Wherein X represents Na, K or NH _4, and 4,4′-diazidostilbene-2,
2'-disulfonate, the following general formula (II)

[0026]

Embedded image

(Wherein X represents Na, K or NH ₄ ), such as bis (4-azido-2-sulfobenzylidene) acetone salt.

The bisazide compounds of the above general formulas (I) and (II) have different spectral sensitivities and slightly different sensitivities, but both are useful and preferably used in the water-soluble photosensitive composition of the present invention. be able to.

In addition to the above, a bis azide compound obtained by a condensation reaction between a cycloketone and an azidobenzaldehyde sulfonate can also be used.
It is easily hydrolyzed and degraded in water, and has the general formula (I) or (I
Compared with the bisazide compound of I), it is inferior in storage stability, and expensive and hard to obtain, so that it is not practical.

Incidentally, in the water-soluble photosensitive composition of the present invention,
The photosensitive bisazide compound is not limited to the above, and any photosensitive bisazide compound can be used as long as it is water-soluble.

In the present invention, the photosensitive bisazide compound may be used alone or in combination of two or more.

The compounding amount of (B) the photosensitive bisazide compound is preferably 1 to 7% by weight, more preferably 2 to 6% by weight, based on (A) the water-soluble polymer. If the compounding amount is larger than the above range, not only the sensitivity is not much improved, but also problems such as deterioration of resolution and precipitation of a photosensitive bisazide compound are caused, which is not preferable.

Conventionally, a photosensitive bisazide compound is blended in an amount of about 10 to 15% by weight with respect to a water-soluble polymer, so that the material cost is increased and the production cost is problematic. By blending the component (a) and the component (b) as the water-soluble polymer, it is possible to further increase the sensitivity, whereby the amount of the photosensitive bisazide compound can be suppressed, and the cost is reduced. Thus, a practical water-soluble photosensitive composition can be obtained.

In the present invention, in addition to the above-mentioned essential components, if necessary, a compatible polymer and various additives,
For example, a coloring agent, a plasticizer, a surfactant, a coupling agent for further increasing the adhesion to the substrate, and the like can be appropriately added and blended. Examples of compatible polymers include, for example, modified polyvinyl alcohol, carboxymethylcellulose, hydroxymethylcellulose, poly-L
A homopolymer such as sodium salt of glutamic acid, gelatin, polyacrylamide, polyvinyl methyl ether, polyvinyl acetal, polyethylene oxide, or an acrylamide-diacetone acrylamide copolymer, acrylamide-vinyl alcohol copolymer, maleic acid-vinyl methyl ether Copolymers such as copolymers can be exemplified, but are not limited thereto. In particular, by blending modified polyvinyl alcohol as a compatible polymer, the peelability of the photoresist pattern can be improved. These modified polyvinyl alcohols only need to show water solubility,
Both partially saponified and completely saponified products can be used. As the modified polyvinyl alcohol, various modified polyvinyl alcohols such as those modified with diacetone acrylamide, acryloylmorpholine, N-vinyl-2-pyrrolidone, and those having a silicone-containing group added to a side chain may be used. Can be. These may be used alone or in combination of two or more.

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

According to the pattern forming method of the present invention, a photocurable pattern is formed on a substrate using the water-soluble photosensitive composition, then a light-absorbing substance is applied on the entire surface, dried, and then the photocurable pattern is formed. The black matrix pattern is formed on the substrate by peeling off the light absorbing material on the substrate.

First, the above-mentioned water-soluble photosensitive composition is dissolved in water so as to have a viscosity of, for example, about 20 to 30 cP / 25 ° C., and used as a coating liquid, which is coated on a glass substrate.

Next, this water-soluble photosensitive composition is applied,
The photoresist layer obtained by drying is exposed through a shadow mask. Exposure is performed with ultraviolet light, particularly at a wavelength of 300 to 40.
A UV lamp that outputs light near 0 nm is suitably used, and the amount of exposure varies slightly depending on the composition of the water-soluble photosensitive composition, but is preferably about 0.5 to 1.5 mW / cm ² . By using the water-soluble photosensitive composition of the present invention, it is possible to obtain a good photocurable pattern exhibiting reciprocity failure characteristics in gap exposure. Although the reason is not clear, 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 and cross-link.
It is said to cause light curing. However, in the nitrene, in the presence of oxygen or water, the crosslinking reaction and the non-crosslinking reaction with oxygen or water coexist, and as a result, the crosslinking reaction is suppressed. Due to the suppression of the crosslinking reaction, a photocuring reaction occurs at a portion corresponding to the center portion of the high-illuminance beam passage hole, while a photocuring reaction is suppressed at a portion corresponding to the peripheral portion of the low-illumination beam passage hole. A photo-cured pattern of dots smaller than the mask through holes (beam passage holes) is obtained. Therefore, the docking phenomenon unlike the conventional example does not occur. However, the sensitivity of the entire photoresist layer is reduced accordingly, and it is necessary to increase the illuminance to obtain a desired dot diameter.
Polyvinyl alcohol (PVA), which is a component, has a low oxygen permeability, so that it blocks oxygen that suppresses the photocuring reaction, and the crosslinking reaction proceeds efficiently even under low illuminance conditions. When the water-soluble photosensitive composition of the present invention is used for contact exposure (exposure performed by bringing a mask into contact with a photoresist layer), it is needless to say that a photo-cured pattern faithful to the mask pattern can be formed. Further, by adding the vinylpyrrolidone-vinylimidazole copolymer (VP-VI copolymer) as the component (a), the effect of preventing a decrease in adhesiveness to a substrate is particularly excellent.

Next, development is performed to remove unexposed portions.
A light curing pattern is formed on a glass substrate. Development can be performed by a known method.

Next, this is dried, and a light-absorbing substance-containing liquid is applied over the entire surface of the photo-cured pattern and the exposed substrate, and dried again. A light-absorbing substance deposited on the pattern is also peeled off to form a black matrix pattern on the substrate. The light absorbing substance is not particularly limited, and generally used graphite is preferably used. The above-described peeling and removal can be performed using a usual peeling agent or the like. As the release agent, for example, hypochlorous acid,
Hypochlorites such as sodium hypochlorite; hydrogen peroxide;
Peroxosulfates such as peroxosulfate and potassium persulfate; periodates such as periodate and potassium periodate; and acidic aqueous solutions such as thiourea, permanganate and sulfamic acid are used. The water-soluble photosensitive composition of the present invention comprises one of these generally known release agents.
Peeling can be easily performed using one or more kinds. The peeling may be performed at room temperature or by heating.

When the black matrix thus obtained is used for a color cathode ray tube, the black matrix holes or stripe portions are filled with three primary color phosphors of red, blue and green, and the panel is irradiated with an electron beam from an electron gun. A desired phosphor is irradiated through a through hole of the shadow mask to obtain a color image. By applying the water-soluble photosensitive composition and the method of forming a black matrix pattern of the present invention, a high-contrast and clear color image can be obtained.

[0043]

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

Example 1 (1) Preparation of Water-Soluble Photosensitive Composition VP-VI copolymer (VP: VI = 99: 1 (mol%)
Ratio), K value = 90), and PVA (degree of saponification: 88 mol%, degree of polymerization: 1050) were each dissolved in water to prepare a VP-VI copolymer and a 7% by weight aqueous solution of PVA.

Next, 90 g of the above 7% by weight aqueous solution of VP-VI copolymer and 10 g of 7% by weight aqueous solution of PVA were mixed to prepare an aqueous solution of a water-soluble polymer of VP-VI copolymer: PVA = 90: 10 (weight ratio). did.

Next, disodium 4,4'-diazidostilbene-2,2'-disulfonate (compound represented by the general formula (I), wherein X is Na) is added to the total weight of the water-soluble polymer. Was added so as to be 5% by weight (0.35 g), and pure water was further added to prepare a water-soluble photosensitive composition having a viscosity of 25 cP / 25 ° C. (coating solution 1).

(2) Formation of Photoresist Layer A washed glass plate was used as a substrate, and the coating solution 1 was spin-coated on the substrate using a spinner, and dried by applying hot air while shaking off. Next, the substrate is taken out and the temperature is set to 50 ° C.
And blow drying with a photoresist layer (0.8 μm thick).
m) was formed.

(3) Exposure A 55 μm slit, 250 mm, was formed on the photoresist layer.
An ultra-high pressure mercury lamp that outputs light near a wavelength of 350 nm through a shadow mask having a dot pattern of holes having a pitch of μm and an exposure dimension of a mask-photoresist interlayer distance (gap) of 6 mm and a lamp-mask distance of 300 mm. ^{2 at} a light intensity of illuminance 0.8mW / cm 2
Point light source exposure was performed for 0 seconds. The substrate temperature was 50 ° C.

(4) Development Next, spray development with pure water was performed for 30 seconds at room temperature (25 ° C.) using a spinner, and then shaken off.
After drying with hot air, a photo-cured pattern was obtained on the substrate.

(5) Formation of Black Matrix Pattern A graphite slurry ("Hitasol GA-66M"; Hitachi) A two-fold diluted solution (diluted with water) of Powder Metallurgy Co., Ltd. was spin-coated, shaken off, and dried with warm air to form a graphite film.

Next, this is immersed in a 17% aqueous solution of sulfamic acid at room temperature (25 ° C.) for 1 minute, and then a high-pressure water spray is sprayed on the graphite film to form a light-cured pattern and graphite on the light-cured pattern. Remove the membrane,
A black matrix pattern was obtained on a glass substrate.
In the obtained black matrix pattern, no peeling of the photocured pattern, no scum and no fringe were observed, holes were formed at positions corresponding to the through holes of the shadow mask, and the resolution was good. .

(Embodiments 2 to 6)
Water-soluble photosensitive compositions (coating solutions 2 to 6) were prepared in the same manner as in Example 1, except that the mixing ratio of -VI copolymer: PVA was changed as shown in Table 1.

Using each of these coating solutions, Example 1 was used.
When the pattern of the black matrix was formed in the same manner as above, the resulting black matrix pattern did not show the peeling of the photo-cured pattern, no scum and fringe was observed, and holes were formed at positions corresponding to the through holes of the shadow mask. It was formed and had good resolution.

(Comparative Examples 1 to 4)
-VI copolymer: PVA mixing ratio, and 4,4'-
Water-soluble photosensitive compositions (comparative coating solutions 1 to 4) in the same manner as in Example 1 except that the blending amounts of diazidostilbene-2,2'-disulfonate were changed as shown in Table 1, respectively. Was prepared.

Exposure and development were carried out using each of these comparative coating solutions in the same manner as in Example 1 above. As a result, no photocurable pattern was obtained with Comparative coating solutions 2 and 4, and the photoresist layer was dissolved during development. have done. In addition, comparative coating liquid 1,
In No. 3, since a photo-cured pattern was obtained, a black matrix was formed in the same manner as in Example 1. The obtained black matrix did not show any peeling residue of the photo-cured pattern and no fringe, and the resolution was low. Although it was good, the sensitivity was remarkably inferior to those of Examples 1 to 6.

Comparative Examples 5 and 6 In Comparative Examples 1 and 2,
A 10% ethyl alcohol solution of a silane coupling agent ("KBM603"; manufactured by Shin-Etsu Chemical Co., Ltd.) is added so that the silane coupling agent is 3% by weight of the total weight of the water-soluble polymer, and the water-soluble polymer is added. Light-sensitive compositions (Comparative Coating Solution 5, Comparative Coating Solution 6) were prepared.

When a black matrix pattern was formed using each of the comparative coating solutions 5 and 6 in the same manner as in Example 1 above, no photocurable pattern was obtained with the comparative coating solution 6, and the photoresist layer was developed during development. It has dissolved. In the comparative coating liquid 5, a photocurable pattern was obtained. Therefore, when a black matrix was formed in the same manner as in Example 1, the resulting black matrix showed some peeling residue of the photocurable pattern and generation of fringes. . The sensitivity was remarkably inferior to those of Examples 1 to 6, and was almost the same as that of Comparative coating liquid 1.

(Embodiment 7) In Embodiment 5, 4,4 '
Diazodostilbene-2,2'-disulfonate disodium to bis (4-azido-2-sulfobenzylidene)
A water-soluble photosensitive composition (coating solution 7) was obtained in the same manner as in Example 5, except that disodium acetone (the compound represented by the general formula (II), X was Na) was used.

When a black matrix pattern was formed using this coating liquid 7 in the same manner as in Example 5, the resulting black matrix pattern showed no peeling of the photo-cured pattern and generation of scum and fringes. However, a hole was formed at a position corresponding to the through hole of the shadow mask, and the resolution was good.

(Embodiment 8) In the fifth embodiment, the VP-V
A water-soluble photosensitive composition (coating solution 8) was prepared in the same manner as in Example 5, except that the I copolymer was changed to the one having VP: VI = 95: 5 and the K value = 90.

When a black matrix pattern was formed using this coating liquid 8 in the same manner as in Example 5, the resulting black matrix pattern did not show any peeling residue of the photocured pattern and no fringe. A hole was formed at a position corresponding to the through hole of the shadow mask, and the resolution was good. However, slight scum was generated without any problem.

Comparative Example 7 In Example 1, PVP was used as the component (A) instead of 100 g of a 7% by weight aqueous solution of a water-soluble polymer comprising a VP-VI copolymer and PVA.
A water-soluble photosensitive composition (Comparative Coating Solution 7) was prepared in the same manner as in Example 1, except that 100 g of 7% by weight (K value = 100) water-soluble was used.

Using the comparative coating solution 7, the above-mentioned Example 1 was used.
When a black matrix pattern was formed in the same manner as in the above, the resulting black matrix pattern had peeling residue of the photocured pattern and generation of fringes, and was poor in resolution. Further, the sensitivity was remarkably inferior to those of Examples 1 to 6, and was almost equal to Comparative Example 1.

(Comparative Example 8) In Example 5, VP-V
A water-soluble photosensitive composition (Comparative Coating Solution 8) was prepared in the same manner as in Example 5, except that the I copolymer was changed to PVP (K value = 100).

Using this comparative coating solution 8, the above Example 5
When a black matrix pattern was formed in the same manner as in the above, the resulting black matrix pattern had peeling residue of the photocured pattern and generation of fringes, and was poor in resolution. Further, the sensitivity was remarkably inferior to those of Examples 1 to 6, and was almost equal to Comparative Example 3.

The sensitivity measurement and storage stability of each of the above Examples and Comparative Examples were evaluated according to the following criteria.

[Sensitivity Evaluation] The black matrix patterns formed in Examples 1 to 8 and Comparative Examples 1, 3, 5, 7, and 8 were evaluated by comparing the hole diameters. The larger the hole diameter is, the higher the sensitivity and the better.

As a result, [(Example 8> Example 5 = Example 7) ≧ Example 6> Example 4> Example 3> Example 2> Example 1] >> ( Comparative Example 3 = Comparative Example 8)> (Comparative Example 1 = Comparative Example 5 = Comparative Example 7).

[Storage stability] The prepared coating solutions (coating solutions 1 to 8 and comparative coating solutions 1 to 8) were stored in a container sealed with nitrogen gas for one week in a dark place at room temperature (25 ° C.). did.

As a result, with respect to the coating liquids 1 to 8 and the comparative coating liquids 1 to 4, 7, and 8, no foreign matter was found,
The storage stability was good. For the comparative coating solutions 5 and 6, the generation of foreign matter was confirmed one day after storage, and after one week, turbidity was generated, and the storage stability was extremely poor.

[0071]

[Table 1]

[0072]

As described above in detail, the water-soluble photosensitive composition of the present invention has good releasability and hardly leaves any peeling, so that it is possible to prevent color mixing due to the adhesion of the phosphor. In addition, even when the water-soluble polymer is a two-component system, a photocurable pattern can be efficiently formed even with a thin film, so that a reduction in material cost can be expected. Also, because of its high sensitivity,
A pattern can be formed in a short time with an exposure amount at low illuminance, thereby improving the throughput. Therefore, the manufacturing cost can be reduced and the manufacturing efficiency can be improved.
High quality products can be manufactured. In addition, even in the case of gap exposure, a docking phenomenon does not occur, and a good photocurable pattern can be obtained in both contact exposure and gap exposure, and wide application is possible. further,
Since it is not necessary to use an additive such as a silane coupling agent which easily generates foreign matter, a product having excellent storage stability of the prepared coating solution and a long service life can be provided. By producing a black matrix using the water-soluble photosensitive composition of the present invention, a high-sensitivity, high-resolution, clear color image can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 139/06 C09D 139/06 G02B 5/00 G02B 5/00 B G03F 7/033 G03F 7/033 H01J 9/227 H01J 9 / 227 D // G02B 5/20 101 G02B 5/20 101 (72) Hiroshi Takanashi 150 Nakamaruko, Nakahara-ku, Kawasaki City, Kanagawa Prefecture

Claims (5)

[Claims] 1. A water-soluble photosensitive composition comprising (A) (a) a vinylpyrrolidone-vinylimidazole copolymer, and (b) a water-soluble polymer comprising polyvinyl alcohol, and (B) a photosensitive bisazide compound. Stuff. 2. The photosensitive bisazide compound (B) is represented by the following general formula (I) or (II): (Wherein X represents Na, K or NH ₄ ) (Wherein, X is Na, K or an NH ₄₎ containing at least one compound represented by claim 1 a water-soluble photosensitive composition. 3. The method according to claim 1, wherein (A) (a) the vinylpyrrolidone-vinylimidazole copolymer is vinylpyrrolidone: vinylimidazole = 99.99: 0.01 to 98: 2 (mol%). Water-soluble photosensitive composition. 4. A vinylpyrrolidone-vinylimidazole copolymer: polyvinyl alcohol = 95: 5 to 30:
The water-soluble photosensitive composition according to any one of claims 1 to 3, which has a weight ratio of 70. 5. After forming a photo-cured pattern on a substrate using the water-soluble photosensitive composition according to claim 1, a light-absorbing substance is applied to the entire surface and dried. A method of forming a black matrix pattern, wherein a black matrix pattern is formed on a substrate by peeling and removing the photocurable pattern and a light-absorbing substance thereon.