JPH1172912A - Water-soluble photosensitive composition and formation of black matrix pattern by using the same - 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, can easily be peeled off without leaving a residue of peeling, has a long life for use and excellent storage stability, as a photoresist, especially to be used for the production of a black matrix of a color CRT and the like. SOLUTION: This water-soluble photosensitive compsn. is prepared by compounding a photosensitive bisazide compd. and a nonphotosensitive polymer containing three kinds of polyvinylpyrrolidone, polyvinylalcohol and vinylpyrrolidone-vinylimidazole copolymers. After a pattern comprising the water-soluble photosensitive compsn. above described is formed and hardened with light, a light-absorbing material is applied all over the pattern and dried. Then the hardened pattern and the light-absorbing material on the pattern are removed by peeling to form a black matrix pattern.

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.

In order to avoid this docking phenomenon, for example, JP-A-48-79970 discloses a method in which polyvinylpyrrolidone is used as a water-soluble polymer in a water-soluble polymer-water-soluble bisazide compound-based water-soluble photosensitive composition. Is disclosed. That is, when using polyvinylpyrrolidone, when the integrated value of light irradiation is a certain value or less,
The cross-linking profile of the photoresist layer has a characteristic that the cross-linking caused by it hardly progresses (“reciprocity failure property”). , The degree of crosslinking is significantly reduced. 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.
That is. However, Japanese Patent Application Laid-Open No.
Water-soluble polymer as disclosed in JP-A-970-
Water-soluble bis azide compounds have excellent resolution but low sensitivity and poor adhesion to the glass substrate, so a water-soluble adhesion enhancer such as a silane coupling agent should be added in a certain amount or more. There must be. 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.

[0008] In addition, a system in which a photosensitive group is introduced into a water-soluble polymer has been proposed as having excellent pattern shape and resolution, but this system has problems in sensitivity and stability, and is not suitable for practical use. It has not been converted.

Therefore, it has been desired to realize a water-soluble photosensitive composition having high sensitivity, good adhesion to a glass substrate, a long service life, and excellent storage stability.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to provide a highly sensitive photoresist for use in the production of a black matrix such as a color cathode-ray tube. A water-soluble photosensitive composition having excellent adhesion, easily peelable, and having no peeling residue, long service life, and excellent storage stability,
And a method of forming a black matrix pattern using the same.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that the water-soluble photosensitive composition based on a non-photosensitive polymer-photosensitive bisazide compound It has been found that the above problems can be solved by using three specific polymers as the photosensitive polymer, and the present invention has been completed based on this finding.

That is, the present invention provides a non-photosensitive polymer containing (A) at least (a) polyvinylpyrrolidone, (b) polyvinyl alcohol, and (c) a vinylpyrrolidone-vinylimidazole copolymer; (B) a photosensitive bisazide compound,
It relates to a water-soluble photosensitive composition.

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

[0014]

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

The non-photosensitive polymer as the component (A) contains at least three kinds of polymers: (a) polyvinylpyrrolidone, (b) polyvinyl alcohol, and (c) vinylpyrrolidone-vinylimidazole copolymer.

(A) The polyvinylpyrrolidone (PVP) preferably has a K value of 80 to 100, particularly preferably 85 to 95. Here, the K value is a value that depends on the molecular weight.

[0017]

(Equation 1)

[0018] (wherein, C is indicates the number of grams of the polyvinyl pyrrolidone contained in the aqueous solution of polyvinylpyrrolidone 100 ml; eta _r indicates the relative viscosity of the polyvinyl pyrrolidone) are those satisfying the relationship represented by. In addition,
In the above formula, the relative viscosity (η _r ) is the specific viscosity of a solution with respect to a solvent, and the viscosity of a solution having a certain concentration (here, a solution in which 1 g of the above-mentioned polyvinylpyrrolidone is dissolved in 100 ml of water) is η, Is defined as 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, and it becomes difficult to form a desired photocurable pattern.

(B) The polyvinyl alcohol (PVA) preferably has a saponification degree 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.

(C) The vinylpyrrolidone-vinylimidazole copolymer (VP-VI copolymer) includes K
Those having a value of 10 to 100 are preferable, and especially 20 to 95.
It is. Here, the K value is a value that satisfies the relational expression represented by the above equation (where C is the number of grams of the vinylpyrrolidone-vinylimidazole copolymer contained in 100 ml of the aqueous solution of vinylpyrrolidone-vinylimidazole copolymer). Read; η _r should be read as the relative viscosity of the vinylpyrrolidone-vinylimidazole copolymer). The reason why the K value is preferably in the above range is the same as the reason described in the above (a).

Further, vinylpyrrolidone (VP): vinylimidazole (VI) = 99.9: 0.1 to 1:99
(Molar% ratio) is preferable, and in particular, 50:50
~ 25: 75 (mole% ratio) is preferred. VP
If the ratio of VI to is smaller than the above range, the effect of improving the adhesion to the glass substrate is not sufficiently exhibited, while if it exceeds the above range, the resolution tends to deteriorate,
Not preferred.

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 these three components (a), (b) and (c) as component (A), the water-soluble photosensitive composition of the present invention improves the adhesiveness and peelability with a glass substrate. This eliminates the need for using a silane coupling agent, thereby improving the service life and storage stability of the coating solution.

The non-photosensitive polymer used as the component (A) in the present invention, besides the above-mentioned components (a), (b) and (c), other non-photosensitive polymers which can be compatible with these components. One or more non-photosensitive polymer substances may be further added.

As such a non-photosensitive polymer substance,
For example, carboxymethylcellulose, hydroxymethylcellulose, sodium salt of poly-L-glutamic acid,
A homopolymer such as gelatin, polyacrylamide, polyvinyl methyl ether, polyvinyl acetal, or polyethylene oxide; or a copolymer such as acrylamide-diacetone acrylamide copolymer, acrylamide-vinyl alcohol copolymer, or maleic acid-vinyl methyl ether copolymer. Examples of the polymer include, but are not limited to, these.

(A) In the non-photosensitive polymer, (c)
The blending ratio of the VP-VI copolymer is preferably in the range of 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, based on the total weight of (a) PVP and (b) PVA. If the compounding ratio of the component (c) is less than the above range, the effect of improving the adhesion to the glass substrate is not sufficient, while if it exceeds the above range, the resolution and the releasability of the photocurable pattern tend to decrease. Is not preferred.

The mixing ratio of (a) PVP and (b) PVA is preferably about PVP: PVA = 95: 5 to 40:60 (weight ratio), more preferably 70:30 to 5: 5.
It is about 0:50. The sensitivity is increased by increasing the blending amount of PVA, but if the blending amount of PVA exceeds the above range, the adhesion to the substrate (mainly, the glass substrate) and the sensitivity are reduced, and the resolution is also deteriorated at the same time. There is a tendency. On the other hand, if it is less than the above range, it is difficult to achieve high sensitivity.

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

[0029]

Embedded image

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

[0031]

Embedded image

In addition to the bis (4-azido-2-sulfobenzylidene) acetone salt represented by the formula (wherein X represents Na, K or NH ₄ ), the following general formula (III)

[0033]

Embedded image

(Wherein, X represents Na, K or NH ₄ ). However, the compound represented by the general formula (III) is easily hydrolyzed in water and deteriorates, and furthermore, the compound represented by the general formula (I)
Compared with the compound represented by the formula (II), the bisazide compounds represented by the general formulas (I) and (II) are inferior in storage stability, difficult to synthesize and expensive. Is preferably used.

In addition to the above, bisazide compounds obtained by the condensation reaction of acetylacetone, methyl ethyl ketone, etc. with azidobenzaldehyde sulfonate can also be used, but the bisazide compounds of the general formulas (I) and (II) can be used. Since the synthesis is more difficult, the cost of raw materials increases accordingly.

The bisazide compounds of the 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. Can be.

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 amount of the photosensitive bisazide compound (B) is preferably 1 to 7% by weight, more preferably 2 to 6% by weight, based on the non-photosensitive polymer (A). 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 compounded in an amount of about 10 to 15% by weight with respect to the non-photosensitive polymer, which increases the material cost and causes a problem in production cost. In the component (A),
By blending the three polymers of component (c), high sensitivity can be achieved at low cost, whereby the amount of the photosensitive bisazide compound can be reduced, and a more inexpensive and practical water-soluble compound can be obtained. An optical composition can be obtained.

In the present invention, in addition to the above essential constituents, 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. 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, and either partially saponified products or 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, after forming a photo-cured pattern using the water-soluble photosensitive composition, a light-absorbing substance is applied on the entire surface, dried, and then the photo-cured pattern and the The black matrix pattern is formed by peeling off the light absorbing material.

First, the above water-soluble photosensitive composition is used as a coating solution by dissolving it in water so as to have a viscosity of, for example, about 20 to 30 cP / 25 ° C., and is applied onto 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 crosslink,
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. Particularly, a polymer containing vinylpyrrolidone, for example, polyvinylpyrrolidone (PVP) as the component (a) is excellent in oxygen permeability, so that in gap exposure, oxygen in the air is efficiently incorporated into the photoresist layer, and In order to suppress the cross-linking reaction by reacting with nitrene in the layer, a photocuring reaction occurs at the portion corresponding to the center of the high-illuminance beam passage hole, while the photocuring reaction occurs at the portion corresponding to the peripheral portion of the low-illuminance beam passage hole. The reaction is suppressed, and as a result, a photocured pattern of dots smaller than the through holes (beam passage holes) of the shadow mask 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 in order to obtain a desired dot diameter. However, polyvinyl alcohol (PVA), which is the component (b) of the present invention, contains oxygen. Since the transmittance is low, oxygen that suppresses the photocuring reaction is blocked, 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. In addition, the vinylpyrrolidone-vinylimidazole copolymer (VP-
(VI copolymer) is excellent in the effect of preventing a decrease in adhesion to a substrate.

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 the light-absorbing substance-containing liquid is applied over the entire surface of the photo-cured pattern and the exposed substrate, and dried again. Then, the photo-cured pattern is peeled off and removed. The black matrix pattern is formed by peeling and removing the light absorbing material deposited on the pattern. 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. Examples of the release 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, acidic aqueous solutions such as thiourea, permanganate and sulfamic acid are used. The water-soluble photosensitive composition of the present invention comprises one or more of these generally known release agents.
Peeling can be easily performed by using more than one kind. 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 stripes are filled with three primary color phosphors of red, blue and green, and this 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.

[0050]

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

Example 1 (1) Synthesis of Water-Soluble Photosensitive Composition PVP (K value = 90), PVA (saponification degree: 88 mol%,
Polymerization degree 1050), VP-VI copolymer (VP: VI
= 90:10 (mol% ratio, K value = 90) was dissolved in water, respectively, and 9 parts of PVP, PVA and VP-VI copolymer were dissolved.
A weight% aqueous solution was prepared respectively.

Next, 90% by weight of the above PVP aqueous solution 90
g, 9 wt% PVA aqueous solution, 10 g, 9 wt% VP-VI
1 g of an aqueous solution of a copolymer is mixed, and PVP: PVA: VP
-VI copolymer = 90: 10: 1 (weight ratio) to prepare an aqueous solution of a non-photosensitive polymer.

Next, disodium 4,4'-diazidostilbene-2,2'-disulfonate (compound represented by the general formula (I), X is Na) was added to the total amount of the non-photosensitive polymer. It was added so as to be 5% by weight (0.45 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 Using a washed glass plate as a substrate, a coating solution 1 was spin-coated on the substrate, and dried by applying hot air while shaking off. Next, the substrate was taken out and dried at 50 ° C. for 15 minutes to form a photoresist layer (0.8 μm in thickness).

(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 is 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, Ltd.) is formed on the entire surface of the glass substrate on which the above-mentioned photocured pattern is formed, on the photocured pattern and on the exposed substrate. 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 was immersed in a 17% aqueous solution of sulfamic acid at 25 ° C. for 1 minute, and then sprayed with a water spray at a pressure of 3 kg / cm ² onto the graphite film to form a light-cured pattern and graphite on the light-cured pattern. The film was removed to obtain a black matrix pattern. In the obtained black matrix pattern, no peeling residue of the photo-cured pattern and generation of fringes were not observed, and holes were formed at positions corresponding to the through holes of the shadow mask, and the resolution was good.

(Examples 2 to 5) In Example 1, the PV
Water-soluble photosensitive compositions (coating solutions 2 to 5) were prepared in the same manner as in Example 1 except that the mixing ratio of P: PVA: VP-VI copolymer was changed as shown in Table 1.

Using each of these coating solutions, Example 1 was used.
When a black matrix pattern was formed in the same manner as above, the resulting black matrix pattern did not show any peeling residue of the light-cured pattern or fringe, and holes were formed at positions corresponding to the through holes of the shadow mask. And the resolution was good.

(Comparative Examples 1 to 7)
Mixing ratio of P: PVA: VP-VI copolymer;
Except that the addition amount of 4'-diazidostilbene-2,2'-disulfonate disodium was changed as shown in Table 1,
In the same manner as in Example 1, water-soluble photosensitive compositions (Comparative Coating Solutions 1 to 7) were prepared.

Exposure and development were performed in the same manner as in Example 1 using each of these comparative coating solutions. As a result, the photo-cured patterns of the comparative coating solutions 1, 2, and 6 peeled off during development. . Further, in the comparative coating solutions 4 and 5, the photocuring reaction did not sufficiently proceed, and a photocurable pattern was not obtained. Since a photocurable pattern was obtained only in Comparative Coating Solutions 3 and 7, a black matrix pattern was formed in the same manner as in Example 1, respectively. No generation was observed and holes were formed at positions corresponding to the through-holes of the shadow mask, and the resolution was good. However, the sensitivity was remarkably inferior to those of Examples 1 to 5. Was.

(Comparative Example 8) In Comparative Example 2, a silane coupling agent ("KBM603"; manufactured by Shin-Etsu Chemical Co., Ltd.)
Was added so that the silane coupling agent was 3% by weight of the total weight of the non-photosensitive polymer, to prepare a water-soluble photosensitive composition (Comparative Coating Solution 8).

When a black matrix pattern was formed using this comparative coating liquid in the same manner as in Example 1, fringes were generated in the obtained black matrix pattern, and the peeling residue of the photocured pattern was also observed. Was done. The sensitivity was remarkably inferior to those of Examples 1 to 5, and was almost the same as that of Comparative coating liquid 3.

(Comparative Example 9) In Comparative Example 6, a silane coupling agent ("KBM603"; manufactured by Shin-Etsu Chemical Co., Ltd.)
Was added so that the silane coupling agent was 3% by weight of the total weight of the non-photosensitive polymer to prepare a water-soluble photosensitive composition (Comparative Coating Solution 9).

When a black matrix pattern was formed using this comparative coating liquid in the same manner as in Example 1, fringes were generated in the obtained black matrix pattern, and the peeling residue of the photocured pattern was also observed. Was done. The sensitivity was remarkably inferior to those of Examples 1 to 5, and was almost the same as that of Comparative coating liquid 7.

Examples 6 to 10 In Examples 1 to 5, disodium 4,4′-diazidostilbene-2,2′-disulfonate was replaced with disodium bis (4-azido-2-sulfobenzylidene) acetone. (Water-soluble photosensitive compositions (coating solutions 6 to 10) were obtained in the same manner as in Examples 1 to 5, except that the compound represented by the general formula (II) was replaced with X). .

Using each of these coating solutions, Example 1 was used.
When a black matrix pattern was formed in the same manner as above, the resulting black matrix pattern did not show any peeling residue of the light-cured pattern or fringe, and holes were formed at positions corresponding to the through holes of the shadow mask. And the resolution was good.

The above Examples 1 to 10 and Comparative Examples 1 to 9
The sensitivity measurement and storage stability were evaluated according to the following criteria.

[Sensitivity Evaluation] The black matrix patterns formed in Examples 1 to 10 and Comparative Examples 3 and 7 to 9 were evaluated by comparing the sizes of the hole diameters.
The larger the hole diameter is, the higher the sensitivity and the better.

As a result, [(coating liquid 4 = coating liquid 9) ≧ (coating liquid 5 = coating liquid 10)> (coating liquid 3 = coating liquid 8)> coating liquid 2 = coating liquid 7 )> Coating liquid 1 = Coating liquid 6)] >>> (Comparative coating liquid 7 = Comparative coating liquid 9)> (Comparative coating liquid 3 = Comparative coating liquid 8).

[Storage stability] Each of the prepared coating solutions (coating solutions 1 to 10 and comparative coating solutions 1 to 9) was placed in a container sealed with nitrogen gas for one week in a dark place at room temperature (25 ° C.). Saved.

As a result, with respect to the coating liquids 1 to 10 and the comparative coating liquids 1 to 7, no generation of foreign matter was observed, and the storage stability was good. As for the comparative coating liquids 8 and 9, generation of foreign matter was confirmed one day after storage, and after one week, turbidity was generated and storage stability was extremely poor.

[0074]

[Table 1]

[0075]

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. Further, since a photocurable pattern can be efficiently formed even with a thin film, a reduction in material cost can be expected. In addition, since the sensitivity is high, a pattern can be formed in a short time with an exposure amount at low illuminance, and the throughput is improved. Therefore, the manufacturing cost can be reduced and the manufacturing efficiency can be improved, and high-quality products can be manufactured. Docking does not occur even in the case of gap exposure,
A good photocurable pattern can be obtained in any of contact exposure and gap exposure, and a wide range of application is possible. Further, since there is no need to use an additive such as a silane coupling agent which easily generates foreign substances, a product having excellent storage stability of the prepared coating liquid 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.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // G02B 5/00 G02B 5/00 B (72) Inventor Hiroshi Takanashi 150 Nakamaruko, Nakahara-ku, Kawasaki-shi, Kanagawa Pref.

Claims (6)

[Claims] 1. A non-photosensitive polymer containing (A) at least (a) polyvinylpyrrolidone, (b) polyvinyl alcohol, and (c) a vinylpyrrolidone-vinylimidazole copolymer, and (B) a photosensitive bisazide compound. A water-soluble photosensitive composition comprising: 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 water-soluble photosensitive composition according to claim 1, wherein the vinylpyrrolidone-vinylimidazole copolymer is contained in an amount of 0.1 to 5% by weight based on the total weight of polyvinylpyrrolidone and polyvinyl alcohol. Stuff. 4. The water-soluble photosensitive composition according to claim 1, wherein polyvinylpyrrolidone: polyvinyl alcohol = 95: 5 to 40:60 (weight ratio). 5. The method according to claim 1, wherein (B) a photosensitive bisazide compound is blended in a ratio of 1 to 7% by weight with respect to (A) a non-photosensitive polymer. Water-soluble photosensitive composition. 6. After forming a photo-curing pattern on a substrate using the water-soluble photosensitive composition according to claim 1, a light-absorbing substance is applied over the entire surface, and dried. A method of forming a black matrix pattern, wherein the black matrix pattern is formed by peeling off the light-curing pattern and the light-absorbing substance thereon.