JP2001100414A - Water-soluble photosensitive composition and production method of graphite screen for color cathode ray tube using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-soluble photosensitive composition excellent in appliability to a glass panel as a photoresist used in the production of a graphite screen for a color cathode ray tube or the like, having high sensitivity, excellent in developability and resolution, capable of forming a fringe-free pattern of a good shape and excellent also in the removability of the photo-cured pattern and to produce a graphite screen using the composition. SOLUTION: (A) A non-photosensitive polymer containing an acrylamide- acryloyl morpholine copolymer and polyvinylpyrrolidone is blended with (B) a photosensitive bisazido compound to obtain the objective water-soluble photosensitive composition. A photo-cured pattern is formed using the composition on the inner face of a glass panel, graphite is applied to the entire face and dried, and then the photo-cured pattern and the resulting graphite film on the pattern are removed to produce the objective graphite screen for a color cathode ray tube.

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 graphite screen for use as a fluorescent screen of a color cathode ray tube, and a method for producing a graphite screen for a color cathode ray tube using the same. More specifically, it is possible to form a uniform coating film with excellent applicability to a glass panel, and to form a pattern having a high sensitivity, excellent developability, excellent resolution, and no fringe. The present invention relates to a water-soluble photosensitive composition having excellent releasability of a cured pattern, and a method for producing a graphite screen for a color CRT using the same.

[0002]

2. Description of the Related Art A graphite screen used as a fluorescent screen of a color cathode ray tube of a color television or the like usually has a graphite pattern made of graphite in a predetermined pattern formed on the inner surface of a glass panel. It forms holes (black matrix holes) or stripes (black stripes). Usually, three primary color phosphors of red (R), green (G), and blue (B) are filled in the black matrix holes or stripes to form three primary color phosphor dots (patterns) or stripes (patterns). At the time of image formation, an electron beam is emitted from an electron gun, and this beam is passed through a number of through holes formed in a shadow mask or through a number of slits formed in an aperture grill. Light is emitted by selectively stimulating the pattern to form a color image on the panel.

[0003] In such a color CRT,
If the positional relationship between each phosphor pattern formed on the inner surface of the glass panel and the through hole (electron beam passage portion) of the shadow mask or the slit portion (electron beam passage portion) of the aperture grill is shifted, the electron beam is irradiated with the desired fluorescent light. The color reproducibility is reduced due to not hitting the body or hitting another phosphor. Therefore, in forming a graphite pattern, 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 accurately corresponding to the through hole of the shadow mask or the slit portion of the aperture grill. Therefore, in general, a shadow mask or an aperture grill used for a color CRT is used as an exposure mask used when forming a graphite pattern.

Usually, in the production of such a graphite screen, first, a water-soluble photosensitive composition is applied to the inner surface of a glass panel to form a photoresist layer, and the photoresist layer is exposed through a shadow mask or an aperture grill. After photo-curing the part, developing and removing the unexposed part to form a photo-cured pattern, apply graphite over the entire surface on the photo-cured pattern and the exposed glass panel and dry to form a graphite film I do. Next, the light-cured pattern is peeled and removed, and the graphite film on the light-cured pattern is also peeled and removed, so that graphite having a matrix hole or a stripe formed at a position corresponding to a hole of a shadow mask or a slit of an aperture grille. Form a pattern. 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 the water-soluble photosensitive composition used for producing such a graphite screen, a polyvinyl alcohol-bichromate type or a water-soluble polymer-water-soluble bisazide compound type has been conventionally used. ing.

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 does not reach the minimum degree of cross-linking required to form a photocurable pattern, and the diameter of the resulting dot or the size of the stripe is the diameter of the dot or the slit of the beam passage. , And no docking occurs.

[0008] However, a water-soluble polymer-water-soluble bisazide compound system disclosed in JP-A-48-79970 is excellent in coatability, developability and resolution, but has low sensitivity and throughput. Is low. In addition, the adhesion to the glass panel is poor, and the photoresist layer is not completely removed at the time of peeling, so that the peeling remains, which results in a graphite pattern with many fringes, or the fluorescent material is formed in the next step of forming the fluorescent material. There is a problem that it adheres to the peeling residue and causes color mixing.

In addition, for example, Japanese Patent Application Laid-Open No. Sho 49-688
No. 01 discloses a photosensitive composition containing a copolymer of acrylamide and diacetone acrylamide (AM-DAAM copolymer) and a photosensitive bisazide compound. This photosensitive composition is excellent in sensitivity and resolution, and can form a graphite pattern with little fringe, but is inferior in coatability to a glass panel and difficult to form a photosensitive film having a uniform film thickness. There is a problem that is. Further, it is difficult to remove the unexposed portion by development, and it takes about twice or more development time as compared with the above-mentioned water-soluble photosensitive composition using polyvinylpyrrolidone. Insufficient development results in residual development on the glass panel, which causes a problem of striation when applying the graphite slurry.

JP-A-6-51509 discloses a photosensitive composition containing a copolymer comprising a water-soluble monomer (eg, acrylamide, diacetone acrylamide, dimethylacrylamide) and acryloylmorpholine, and a water-soluble azide compound. ing.

Among them, a photosensitive composition containing an acrylamide-acryloylmorpholine (AM-ACMO) copolymer has good coatability on a glass panel,
In addition, it has high sensitivity and is easy to remove by development, but has poor resolution and has a problem that a graphite pattern to be formed has many fringes and a good pattern shape cannot be obtained. Also,
Dimethylacrylamide-acryloylmorpholine (D
(MAM-ACMO) The photosensitive composition containing the copolymer has good coatability on a glass panel,
The sensitivity is low, the resolution is inferior as described above, the graphite pattern formed has many fringes, and a good pattern shape cannot be obtained. Further, acrylamide-diacetoneacrylamide-acryloylmorpholine (AM-DAAM-
The photosensitive composition containing the (ACMO) copolymer has good applicability to a glass panel, but has low sensitivity, is inferior in resolution as described above, has many fringes in the graphite pattern formed, and has a good pattern. There is a problem that a shape cannot be obtained.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photoresist for use in the production of a graphite screen for a color cathode ray tube, which is capable of forming a uniform coating film having excellent coatability on a glass panel and high sensitivity. so,
Provided is a water-soluble photosensitive composition which is excellent in developability and resolution, can form a pattern having a good shape without fringes, and has excellent peelability of a photocurable pattern, and a method for producing a graphite screen using the same. It is in.

[0013]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a water-soluble photosensitive composition containing a specific non-photosensitive polymer and a photosensitive bisazide compound is used. As a result, the inventor has found that the above problem can be solved, and based on this finding, has completed the present invention.

That is, the present invention relates to a water-soluble photosensitive composition containing (A) a non-photosensitive polymer containing an acrylamide-acryloylmorpholine copolymer and polyvinylpyrrolidone, and (B) a photosensitive bisazide compound.

Further, the present invention provides a method for forming a photocurable pattern on a glass panel using the above water-soluble photosensitive composition.
After applying graphite on the entire surface and drying, the photocurable pattern and the graphite coating thereon are peeled off to form a graphite pattern,
The present invention relates to a method for producing a graphite screen for a color cathode ray tube.

[0016]

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

In the water-soluble photosensitive composition of the present invention (hereinafter simply referred to as "photosensitive composition"), the non-photosensitive polymer as the component (A) is an acrylamide-acryloylmorpholine copolymer and polyvinylpyrrolidone. Contains species of macromolecules.

In the acrylamide-acryloylmorpholine copolymer (AM-ACMO copolymer), acrylamide (AM) and acryloylmorpholine (AC
The copolymerization ratio (molar ratio) of MO) is preferably about 1 to 5 mol, and particularly preferably about 2 to 3 mol, for 1 mol of ACMO. If the copolymerization ratio of AM to ACMO is too small, the sensitivity tends to be inferior. On the other hand, if the ratio of AM is too large, the gas permeability tends to be low, and the reciprocity failure property tends to be inferior.

As the mode of copolymerization of the AM-ACMO copolymer, any mode such as random copolymerization, block copolymerization, and graft copolymerization is possible, but random copolymerization is preferred. The polymerization degree is not particularly limited, and various polymerization degrees can be selected. However, from the viewpoint of applicability of the photosensitive composition to a glass panel, the viscosity of a 3% by weight aqueous solution of the copolymer is 50%. A polymerization degree of about 150 to 150 cP / 25 ° C. is preferable.
/ 25 ° C. is preferred.

The polyvinyl pyrrolidone (PVP) has a K value of 60 to 60 from the viewpoint of applicability to a glass panel.
100 is preferable, and especially 70-90 is preferable. Here, the K value is a value that depends on the molecular weight,
Equation 1 below

[0021]

(Equation 1)

[0022] (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. A higher K value indicates a higher molecular weight. 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 polyvinylpyrrolidone is dissolved in 100 ml of water) is defined as η, Assuming that the viscosity of the solvent is η _o , the relative viscosity (η _r ) can be obtained 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 photocurable pattern having a desired size.

By blending the two components of the above-mentioned AM-ACMO copolymer and PVP as the component (A), the applicability and peelability of the photosensitive composition of the present invention to a glass panel can be improved. High-sensitivity, high-resolution, fringe-free pattern formation has become possible.

In the component (A), the mixing ratio of the AM-ACMO copolymer is such that
The total weight of VP is preferably about 0.2 to 0.9 (weight ratio), and more preferably about 0.4 to 0.9 (weight ratio). If the blending ratio of the AM-ACMO copolymer is too small, the sensitivity and the releasability of the photocurable pattern tend to be poor. On the other hand, if the blending ratio is too large, the gas permeability tends to be low and the reciprocity failure property tends to be poor. .

Incidentally, in the solid content of the photosensitive composition of the present invention,
The compounding amount of the component (A) is preferably about 50 to 97% by weight, particularly about 60 to 80% by weight.

As the photosensitive bisazide compound as the component (B), a water-soluble one is used, for example, the following general formula (I)

[0027]

Embedded image

Wherein X represents H, Na, K or NH ₄ , wherein 4,4′-diazidostilbene-2,
2'-disulfonic acid or a salt thereof, represented by the following general formula (II)

[0029]

Embedded image

Bis (4-azido-2-sulfobenzylidene) acetone represented by the formula (wherein X represents H, Na, K or NH ₄ ) or a salt thereof is preferably used.
The following general formula (III)

[0031]

Embedded image

2,5-bis (4-azido-2-sulfobenzylidene) cyclopentanone represented by (where X represents H, Na, K or NH ₄ ) or a salt thereof can also be used. .

In addition to the above, bisazide compounds obtained by a condensation reaction of acetylacetone, methyl ethyl ketone, etc. with azidobenzaldehyde sulfonate can also be used, and the compounds represented by the above general formulas (I) to (III)
Since the synthesis is more difficult than the bisazide compound, the raw material cost is increased accordingly. Among them, the above general formula (I),
The bisazide compounds (II) have different spectral sensitivities and slightly different sensitivities, but both are useful in the photosensitive composition of the present invention and can be preferably used.
In particular, the bisazide compound represented by the general formula (I)
Inexpensive and most commonly used.

The photosensitive composition of the present invention is not limited to the above-mentioned photosensitive bis azide compound, and any photosensitive bis azide compound which is water-soluble can be used. In addition, since photosensitive bisazide compounds have different ultraviolet-visible absorption spectra, depending on the type of light source used for exposure, or to compensate for the decrease in sensitivity when using an optical filter, alone or in combination as necessary Can be used.

The amount of the component (B) is preferably 3 to 15% by weight, more preferably 4 to 10% by weight, based on the component (A). If the amount of the component (B) is more than the above range with respect to the component (A), not only the sensitivity does not improve much but also problems such as deterioration of resolution and precipitation of a photosensitive bisazide compound are caused. Therefore, it is not preferable. In the present invention, the blending amount of the component (B) can be suppressed as described above, so that the material cost can be reduced, and a more inexpensive and practical photosensitive composition can be obtained.

In the present invention, in addition to the above-mentioned essential components, if necessary, compatible polymers and various additives,
For example, a coloring agent, a plasticizer, a surfactant, a silicone coupling agent for further improving the adhesion to the glass panel, and the like can be appropriately added and blended.

Since the photosensitive composition of the present invention has good adhesiveness to a glass panel, a small amount of the silicone coupling agent is sufficiently effective when a silicone coupling agent is added. As such a silicon coupling agent, for example, an organic silicon-based material can be mentioned.
03 "(manufactured by Shin-Etsu Silicon Co., Ltd.) and" A1150 "(manufactured by Nippon Unicar Co., Ltd.).

Next, a method for producing a graphite screen for a color cathode ray tube according to the present invention using the photosensitive composition of the present invention will be described.

According to the method for producing a graphite screen for a color cathode ray tube of the present invention, a photocuring pattern is formed on the inner surface of a glass panel using the photosensitive composition, then the graphite is applied on the entire surface, dried, and then the photocuring is performed. By exfoliating and removing the pattern and the graphite coating thereon to form a graphite pattern, a graphite screen for a color cathode ray tube is produced.

First, the photosensitive composition of the present invention is diluted with 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 applied to the inner surface of a glass panel.

In forming a graphite pattern, a dry film of the photosensitive composition must be formed on the inner surface of the glass panel with a uniform thickness. As a coating means therefor, there are a spin coating method, a curtain coating method, a spray method and the like, and the spin coating method is generally used.

In this spin coating method, the flow characteristics of the coating liquid are important. A photosensitive composition containing polyvinylpyrrolidone as a main component (PVP-based composition) has a very good coatability because it is close to a so-called Newtonian fluid, and when a surfactant is used for improving coatability, a very small amount is added. Amount is fine.

On the other hand, a photosensitive composition containing an acrylamide-diacetone acrylamide (AM-DAAM) copolymer as a main component as shown in the conventional example is a non-Newtonian fluid and has poor fluidity and poor coatability. Therefore, in use, a large amount of a surfactant or a water-soluble organic solvent must be added to improve the coating properties, but the coating properties are still considerably inferior to those of the PVP system.

The photosensitive composition of the present invention comprises an AM-DAAM
It has excellent flow characteristics as compared with the copolymer system, exhibits the same flowability as the PVP system, and has good coatability. In addition, since it has higher sensitivity than PVP-based resin, and is excellent in resolution and releasability of a photocurable pattern, a graphite pattern having a good shape can be formed.

Next, the photoresist layer obtained by applying and drying this photosensitive composition is exposed through a shadow mask or an aperture grill. For the exposure, an ultra-high pressure mercury lamp which outputs ultraviolet light, particularly light having a wavelength of about 300 to 400 nm, is preferably used, and the exposure amount is slightly different depending on the composition of the photosensitive composition, but is preferably 0.1 to 1.5 mJ. / C
m ² is preferable. By using the 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. In particular, a polymer containing vinylpyrrolidone, for example, polyvinylpyrrolidone (PVP), which is an essential component in the component (A), has excellent oxygen permeability, so that in the gap exposure, oxygen in the air is efficiently used in the photoresist layer. In order to suppress the crosslinking reaction by reacting with nitrene in the photoresist layer,
The photo-curing reaction occurs at the portion corresponding to the central portion of the high-illuminance beam passage portion, while the photo-curing reaction is suppressed at the portion corresponding to the peripheral portion of the low-illuminance beam passage portion. Area) or a light curing pattern of dots or stripes smaller than the stripe part (beam passage part) of the aperture grille. 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 pattern size. However, AM-, which is another essential component of the component (A) of the present invention, is required. ACMO copolymers are particularly useful for ACM
When the copolymerization ratio of AM to O is about 1 to 5 (molar ratio), high sensitivity can be achieved while maintaining good oxygen permeability, so that the crosslinking reaction proceeds efficiently even under low illuminance conditions. I do. When the 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 photocured pattern faithful to the mask pattern can be formed.

Next, development is performed to remove unexposed portions.
A light curing pattern is formed on the inner surface of the glass panel. Development can be performed using water by a known method.

Next, this was dried, a graphite-containing liquid (graphite slurry) was applied over the entire surface of the photocured pattern and the exposed glass panel, and dried again. Then, the photocured pattern was peeled off and removed. A graphite pattern is formed by exfoliating and removing the graphite adhered on the photocured pattern. The graphite is not particularly limited, and graphite generally used for producing a graphite screen for a color cathode ray tube is preferably used. The above-described peeling and removal can be performed using a usual peeling agent or the like. Examples of the releasing agent include hypochlorites such as hypochlorous acid and sodium hypochlorite; hydrogen peroxide; peroxosulfates such as peroxosulfuric acid and potassium peroxosulfate; periodic acid and potassium periodate; In addition to periodate, an acidic aqueous solution such as thiourea, permanganate, or sulfamic acid is used, and a mixed aqueous solution of hydrogen peroxide, thiourea, and sulfamic acid is preferable. The photosensitive composition of the present invention can be easily peeled by using one or more of these generally known release agents. Also, as the peeling conditions,
It may be performed at normal temperature or may be performed by heating.

When the thus obtained graphite screen 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 radiated through a through hole of a shadow mask or a stripe portion of an aperture grill to obtain a color image. By applying the photosensitive composition of the present invention and the method for producing a graphite screen for a color cathode ray tube, a high-contrast and high-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.

1. Preparation of photosensitive composition

(Synthesis Example 1: Synthesis of AM-ACMO copolymer) 420 g (5.9 mol) of acrylamide and 280 g (2.0 mol) of acryloylmorpholine were added to pure water 9
This was dissolved in 300 g, and this was charged into a three-necked flask, and heated to 53 ° C. while purging with nitrogen gas.

Next, a liquid obtained by dissolving 1.4 g of a polymerization initiator (“VA044”, manufactured by Wako Pure Chemical Industries, Ltd.) in 5 g of pure water was added thereto, and a polymerization reaction was carried out for 3 hours to give acrylamide-acryloylmorpholine ( AM-ACMO) copolymer was synthesized.

The synthesized AM-ACMO copolymer has 3
The viscosity of the weight% aqueous solution was 100 cP / 25 ° C.

(Preparation Example 1: Preparation of Photosensitive Composition 1) A part of the aqueous solution of the AM-ACMO copolymer obtained in Synthesis Example 1 was diluted with pure water to adjust the concentration to 1.5% by weight, and this adjustment was performed. 4,4'-diazidostilbene-2,2 'in 1 kg of liquid
Disodium disulfonate (general formula (I); X = N
a) 1.2 g (8% by weight of AM-ACMO copolymer)
Was added to prepare a photosensitive composition 1.

(Preparation Example 2: Preparation of photosensitive composition 2)
To 1 kg of a 3.0% by weight aqueous solution of VP (K value 90) is added 4,
2.4 g of 4'-diazidostilbene-2,2'-disulfonate disodium (general formula (I), X = Na) (PV
P (8% by weight of P) was added to prepare photosensitive composition 2.

(Preparation Examples 3 to 5: Preparation of Photosensitive Compositions 3 to 5) Photosensitive composition 2 [PVP +] obtained in Preparation Example 2 above
(B) component] was diluted twice with pure water.

This diluent was mixed with the photosensitive composition 1 [AM-ACMO copolymer + component (B)] obtained in Preparation Example 1 in a ratio (weight ratio) shown in Table 1 to obtain a photosensitive composition. Compositions 3-5 were prepared.

[0059]

[Table 1]

(Synthesis Example 2: Synthesis of AM-DAAM copolymer) 317 g (4.46 mol) of acrylamide and 383 g (2.26 mol) of diacetone acrylamide were obtained.
This was dissolved in 9300 g of pure water, and this was charged into a three-necked flask and heated while substituting with nitrogen gas, and the temperature was raised to 50 ° C.

Next, a liquid prepared by dissolving 1.4 g of a polymerization initiator (“VA044”, manufactured by Wako Pure Chemical Industries, Ltd.) in 5 g of pure water was added thereto, and a polymerization reaction was carried out for 3 hours to give acrylamide-diacetoneacrylamide. (AM-DAAM) copolymer was synthesized.

The synthesized AM-DAAM copolymer has 3
The viscosity of the weight% aqueous solution was 120 cP / 25 ° C.

(Preparation Example 6: Preparation of Photosensitive Composition 6) A part of the aqueous solution of the AM-DAAM copolymer obtained in Synthesis Example 2 was diluted with pure water to adjust the concentration to 1.5% by weight. 4,4'-diazidostilbene-2,2 'in 1 kg of liquid
Disodium disulfonate (general formula (I); X = N
a) 1.5 g (10% by weight of AM-DAAM copolymer) was added to prepare photosensitive composition 6.

2. Formation of Photoresist Layer For 1 kg of each of the above photosensitive compositions 1 to 6, 4 g of a nonionic surfactant ("LT-221"; manufactured by NOF Corporation) and a silicon coupling agent ("KBM6")
03 "; Shin-Etsu Silicon Co., Ltd.) (4 g), and coating solutions 1 to 6 were prepared.

Each of the coating solutions 1 to 6 was spin-coated on the inner surface of the degreased glass panel, and dried to form a photoresist layer (dry film). The film thickness was 0.4 μm for coating solutions 1 and 3 to 6 and 0.8 μm for coating solution 2.
, Respectively.

3. Exposure 55 μm slit, 250 μm on the photoresist layer
An ultra-high pressure mercury lamp that outputs light near a wavelength of 350 nm through an aperture grill having slit holes of a μm pitch under an exposure condition of a mask-photoresist interlayer distance (gap) of 4 mm and a lamp-mask distance of 300 mm. Point light source exposure was performed for 10 seconds with a light intensity of 0.07 mW / cm ² through the mask (exposure amount: 0.7 mJ /
cm ² ). The glass panel temperature was 40 ° C.

4. Development Next, weak shower-type development using pure water was performed for 30 seconds at room temperature (25 ° C.) using a spinner, and then shaken off and dried with warm air to obtain a photocured pattern on the inner surface of the glass panel.

5. Formation of Black Stripe Pattern A graphite slurry ("Hitasol GA-66M"; manufactured by Hitachi Powdered Metals Co., Ltd.) is formed on the inner surface of the glass panel on which the above-described photo-cured pattern is formed, on the photo-cured pattern and over the entire surface of the exposed glass panel. ) Was spin-coated with a two-fold dilution (water-diluted solution) and heat-treated at 50 ° C. for 30 minutes to form a dry graphite coating.

Next, the glass panel on which the graphite coating was formed was placed in a 1: 9 (weight ratio) mixed solution of an aqueous solution containing 10% of sulfamic acid and 10% of thiourea and a 10% aqueous hydrogen peroxide solution. After immersion for one minute in the glass panel, the photocured pattern and the graphite coating on the photocured pattern were removed by spray cleaning with pure water to obtain a graphite screen having a black stripe pattern formed on the inner surface of the glass panel. .

With respect to the formation of this black stripe, the sensitivity, developability, resolution, and peelability of the glass panel were evaluated according to the following criteria. Table 2 shows the results.

[Evaluation of Sensitivity] When the slit size of the black stripe was larger than the mask size and no reciprocity failure property was observed, the result was evaluated as XX.

Further, although reciprocity failure characteristics were observed,
A sample having a small slit size and low sensitivity was designated as x.

A sample having reciprocity failure characteristics, a large slit size, and high sensitivity was rated as ○.

[Evaluation of Developability] A sample in which radial coating unevenness was observed on the surface of the black stripe or uneven coating was observed at the periphery of the glass panel due to the undeveloped photosensitive composition was evaluated as x. A sample in which such unevenness was not observed at all was evaluated as ○.

[Evaluation of Resolution] When a fringe was generated in the slits of the black stripes or when the dimensions of the slits were irregular, the cross was evaluated as x. When no fringe was generated and no irregularities were observed, the sample was marked as “○”.

[Evaluation of Peeling Property] The result of the peeling of the photosensitive composition on the glass panel was evaluated as x. When no peeling residue occurred, it was evaluated as ○.

[0077]

[Table 2]

Each of the compositions 1 to 6 had good applicability to a glass panel.

[0079]

As described in detail above, the 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 phosphor adhesion. 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, it is excellent in developability and resolution, and can form a pattern having a good shape without fringe. By producing a graphite screen for a color cathode ray tube using the photosensitive composition of the present invention, it is possible to obtain a high-sensitivity, high-resolution, clear color image.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 39/06 C08L 39/06 G02B 5/20 101 G02B 5/20 101 G03F 7/008 G03F 7/008 7 / 40 521 7/40 521 7/42 7/42 (72) Inventor Tetsuya Nakajima 150 Nakamaruko, Nakahara-ku, Kawasaki-shi, Kanagawa Prefecture F-term in Tokyo Keika Kogyo Co., Ltd. 2H025 AA01 AA02 AA03 AA04 AB17 AC01 AD01 BA07 CB06 CB15 CB53 DA18 DA19 FA03 FA17 FA39 FA48 2H048 BA11 BA45 BA47 BA48 BB41 2H096 AA27 BA02 BA20 CA20 GA08 HA30 JA04 LA02 LA16 4J002 BG07W BG13W BJ00X EQ036 EV236 EV256 FD340 GH00 GP03 GQ00

Claims (7)

[Claims] 1. A water-soluble photosensitive composition comprising (A) a non-photosensitive polymer containing an acrylamide-acryloylmorpholine copolymer and polyvinylpyrrolidone, and (B) a photosensitive bisazide compound. 2. The water-soluble photosensitive composition according to claim 1, wherein in the component (A), the copolymerization ratio (molar ratio) of acrylamide and acryloylmorpholine constituting the copolymer is acrylamide / acryloylmorpholine = 1 to 5. . 3. The component (A), wherein the copolymer is used in an amount of 0.2 to 1 based on the total weight of the copolymer and polyvinylpyrrolidone.
The water-soluble photosensitive composition according to claim 1 or 2, which is contained at a ratio of from 0.9 to 0.9 (weight ratio). 4. A 3% by weight aqueous solution of the copolymer has a viscosity of 5%.
The water-soluble photosensitive composition according to any one of claims 1 to 3, which has a temperature of 0 to 150 cP / 25 ° C. 5. Component (B) is a compound represented by the following general formula (I) or (I)
I) (Wherein X represents H, Na, K or NH ₄ ) (Wherein X represents H, Na, K or NH ₄ ), and contains at least one compound represented by the formula:
The water-soluble photosensitive composition according to any one of the above. 6. The amount of component (B) is 3 to 1 with respect to component (A).
The water-soluble photosensitive composition according to any one of claims 1 to 5, which is blended at a ratio of 5% by weight. 7. After forming a photo-curing pattern on a glass panel using the water-soluble photosensitive composition according to claim 1, graphite is applied to the entire surface, dried, and then the light is cured. A method for producing a graphite screen for a color CRT, wherein a cured pattern and a graphite coating thereon are peeled off to form a graphite pattern.