TW473649B - Photosensitive compositions and pattern formation method - Google Patents

Abstract

Photosensitive compositions prepared without use of a chromium compound. The compositions exhibit high resolution and satisfactory sensitivity, and do not cause environmental pollution. The photosensitive compositions contain a water-soluble azide compound which serves as a photocrosslinking agent and poly(N-vinylacetamide) that is photocrosslinkable in the presence of the water-soluble azide compound.

Description

V7364B A7 B7 V. Description of the Invention (1) Background of the Invention Field of the Invention. 1 The present invention relates to a photosensitive composition, and particularly to water-solubility suitable for forming a black matrix of a color filter, a phosphor pattern, and a color cathode ray tube. Sexy light composition. Description of the Conventional Technology Conventionally, a negative photoresist for forming a black matrix and a phosphor pattern of a color cathode ray tube or the like is an anticorrosive agent including a water-soluble polymer such as polyvinyl alcohol, and dichromate. (Called PVA-ADC based corrosion inhibitor). This type of photobilitizer has the fundamental disadvantage of requiring special treatment equipment to prevent environmental pollution, which may be caused by the presence of dichromate. Printed by the Women ’s Workers ’Cooperatives of the Ministry of Intermediate Standards and Leather Industry (please read the precautions on the back before filling this page). Regarding the photoresist without the problem on K, it is known to contain water Diazide compounds such as 4,4'-diazidostilbene-2,2'-disulfonate (hereinafter referred to as DAS), and in the presence of water-soluble diazide compounds Photo-crosslinkable photosensitive compound of water-soluble polymer. For example, * It has been proposed to include a vinyl alcohol-maleic acid copolymer or a salt thereof (Japanese Patent Laid-Open Application No. 48-97602), a vinyl alcohol-acrylamide copolymer (Japanese Patent Laid-Open Application No. 4 8-9 7 6 0 3), or water-soluble polyvinyl butyral (Japanese Patent Laid-open Application No. 0.4-9 8 9 0 5) is a photosensitive composition of a polymer matrix. However, in practice, these compositions cannot be used because of their low sensitivity. At present, known compositions having sufficient sensitivity include compositions containing polyvinylpyrrolidone (M hereinafter referred to as PVP) and water-soluble two-disc nitride compounds as additives (a composition of this type) Referred to as PVP-DAS-based anti-solar agent; see, this paper standard uses Chinese S inscriptions (('NS) Λ4 size (210 X 297 public 漦) -Λ-473649 A7 B7 V. Description of the invention (2) For example , Japanese Patent Laid-open Application No. 0.48-9 0 1 8 5), K and acrylamide-dipropylene ring acrylamide copolymer (M abbreviated as PAD) and a water-soluble two as an additive I Composition of azide (hereinafter, this type of composition is referred to as PAD-DAS-based corrosion inhibitor; see, for example, Japanese Patent Laid-Open Application No. 50-33764). When using PVA-ADC-based corrosion inhibitor in When forming the black matrix of a color cathode ray tube, due to its low oxygen permeability and lack of reciprocity-law failure characteristics, it has the disadvantage of poor resolution in addition to the aforementioned environmental pollution problems. Conversely, when Use PVP-DAS based In the case of an etchant, due to its excessively high oxygen permeability, proper sensitivity cannot be obtained unless the thickness of the coating film is increased. Increasing the thickness sequentially reduces the resolution. On the other hand, PAD-DAS-based corrosion inhibitors It has excellent sensitivity and resolution, but when it is subjected to the formation of an anti-corrosion pattern and coated with graphite, it provides poor etching characteristics, and depending on the type of graphite, it may not be able to be etched. Regarding the phosphor pattern, PVA- ADC-based corrosion inhibitors are unsatisfactory in terms of environmental pollution and sensitivity. In addition, the residual chromium oxide after combustion will degrade the brightness of adjacent light. In this regard, PVP-DAS-based corrosion inhibitors and PADs -DAS-based corrosion inhibitors have shortcomings in sensitivity and cannot be used.-At the same time, they are known to form phosphor patterns and contain unmodified polyvinyl alcohol and a fourth ammonium salt (for example, styrylfluorene). The photoresist prepared by the condensation reaction between pyridine_salt or styryl sulfonium fiber salt is a non-chromium uranium inhibitor (Japanese Patent Laid-Open Application No. 0.55-2 3 1 6 3, 5 5-6 2 9 0 5 and 5 6-1 1 9 0 6). However, the resolution of these corrosion inhibitors does not make this paper scale NS) M size (210X 297mm) r -5-(Please read the precautions on the back before filling out this page) > Packing. 473649 Intermediate standard elimination of the Ministry of Economic Affairs and private printing A7 B7 V. Description of the invention (3) Satisfied. As mentioned earlier, there are no conventional photoresists that simultaneously satisfy the requirements regarding environmental pollution, sensitivity, I, and resolution. Therefore, there is still a need for novel corrosion inhibitor materials that exhibit excellent characteristics. SUMMARY OF THE INVENTION In view of the foregoing, it is an object of the present invention to provide a photosensitive composition that does not cause environmental pollution and exhibits high resolution and satisfactory sensitivity. In order to overcome the foregoing disadvantages, a first mode of the present invention relates to a photosensitive composition including a water-soluble azide compound as a photo-crosslinking agent, and a photo-crosslinkable compound in the presence of a water-soluble azide compound. Poly (N-vinylacetamide). In the second mode of the present invention, the photosensitive composition according to the first mode further includes another water-soluble polymer that is photo-crosslinkable in the presence of the aforementioned water-soluble azide compound. In the third mode of the present invention, the photosensitive composition according to the second mode includes a water-soluble polymer, and the water-soluble polymer includes a member selected from the group consisting of polyvinylpyrrolidine, acrylamide, and dipropylamine At least one of a copolymer, poly (N, N-dimethylacrylamide), and N, N-dimethylacrylamide-acrylamide copolymer. In the fourth mode of the present invention, the photosensitive composition according to any one of the first to third modes further includes an additive and at least one water-soluble polymer. In the fifth mode of the present invention > a pattern forming method is provided, which includes forming a photosensitive composition layer on a substrate by coating the photosensitive composition according to any one of the first to fourth modes; The composition layer is suitable for the substrate and the paper size] [National Valve House Standard] (('NS) M specifications (210 × 297 mm) e (Please read the precautions on the back before filling this page) UT- ;, '贽 合 竹 衣 印 ¥ 473649 A7 B7 V. Description of the invention (4) Exposure of the pattern; and then using water or an aqueous developer to make the resulting exposure layer visible. | In the present invention In the sixth mode, the aforementioned substrate used in the method according to the fifth mode is used as the inner surface of the panel of the color cathode ray tube. The seventh mode of the present invention relates to a photosensitive composition for forming a black matrix, wherein The composition forms a black matrix of a color cathode ray tube, and includes a water-soluble azide compound as a photo-crosslinking agent, and a water-soluble polymer that is photo-crosslinkable in the presence of the water-soluble azide compound, wherein Of the foregoing The photocrosslinkable water-soluble polymer mainly contains poly (N-vinylacetamide), and it also contains another one which has more prominent reciprocity law failure characteristics than the corresponding poly (N-vinylacetamide). Water-soluble polymer In the eighth mode of the present invention, the water-soluble polymer contained in the photosensitive composition according to the seventh mode is selected from the group consisting of polyvinylpyrrolidine, acrylamide-diacetone acrylamide At least one of a copolymer, poly (N, N-dimethylacrylamide), and an N, N-dimethylacrylamide-acrylamide copolymer. A ninth mode of the present invention relates to phosphorescence formation. A photosensitive composition of a body pattern, wherein the composition comprises a water-soluble azide compound as a photo-crosslinking agent; a water-soluble polymer that can be photo-crosslinked in the presence of the water-soluble azide compound; and a phosphor; And it is prepared by dissolving or dispersing these ingredients in an aqueous medium, wherein the aforementioned photo-crosslinkable water-soluble polymer comprises poly (N-vinylethenylamine). In a tenth mode of the present invention , Used to form according to the ninth horizontal formula The photosensitive composition of the photobody pattern further includes at least one selected from the saponified product of polyvinyl acetate or an acrylic emulsion. I Paper scale Dizhou House Marker (('NS) Λ 4 gauge (210 × 297 mm) --- t --- U --- install ----- ·; ~ order ------ (Please read the precautions on the back before filling this page) 473649 A7 B7 V. Description of the invention (5) The eleventh mode relates to a photosensitive composition for forming a color filter, wherein the composition contains a water-soluble azide as a photo-crosslinking agent.

I compounds; water-soluble polymers that are photocrosslinkable in the presence of water-soluble azide compounds; and pigments; and are prepared by dissolving or dispersing these ingredients in an aqueous medium, wherein the foregoing may be The photocrosslinkable water-soluble polymer contains poly (N-vinylacetamide). In the twelfth mode of the present invention, the photosensitive composition for forming a color device according to the eleventh mode further includes at least one selected from a saponified product of polyvinyl acetate or an acrylic emulsion. The present invention does not use a chromium compound, but provides a photosensitive composition that does not cause environmental pollution and exhibits high resolution and satisfactory sensitivity. The present invention K has discovered that it is possible to obtain a poly (N-vinylacetamidamine) (called p-NVA) which is not used in this field, and a water-soluble azide compound as a photocrosslinking agent. A satisfactory photosensitive composition was completed. The p-NVA which can be used in the present invention has a molecular weight of 100,000-4,000,000, in terms of sensitivity, film formation, etc. (GPC (gel permeation chromatography) analysis: reduction to starch Polymer) and viscosity (300-70,000 centipoise (cp) Consumer Co-operation of the Central Bureau of Standards, Ministry of Economic Affairs. Co-printed by the society (7% solution, 25 ° C)). Water-soluble azide compounds that can be used in the present invention include, but are not limited to, the compounds represented by the chemical formulas described below. 8 (Please read the precautions on the back before filling out this page) The size of the paper is inquired about China ’s K house ticks (rNS) M gauge (2 丨 0X 297 mm) 473649 A7 B7 V. Description of the invention (6) (Chemical formula 1 )

N3

OH — μ · -0Η ~ s〇3x x〇3s (Chemical Formula 3) N3

CH = S03X -CH =

N3 " Dibuzhong "# " Bureau staff negative load 0 · ^ 印 ^^ (Chemical Formula 4) N3

n3 (Chemical Formula 5) The paper standard 垧 川 中 中 g family standard 嘹 ((’NS) Λ4 size (2IOX 297 mm) (Please read the precautions on the back before filling this page)

9 473649 A7 B7 V. Description of the invention (7

n3 (Chemical Formula 6)

CH = CH- -ch3 ch3 (Chemical Formula 7)

n3 ~ C

C—CH = CH- II o

-coox (Please read the notes on the back before filling out this page) • i.

1T (Chemical Formula 8)

CH = CH—C

O " 〇 β-τ · Consumer Cooperatives' Seal (Chemical Formula 9) n3-

xo3s This paper is a Chinese standard house tick ((’NS) Λ4 size (21 OX 297 mm)

N3 10-473649 A7 B7 V. Description of the invention (8) (Read the precautions on the back before filling this page) where X represents lithium, sodium, potassium, ammonium, monoalkylammonium, dialkylammonium, trialkyl Ammonium, or tetraalkylammonium. In addition, water-soluble azide compounds include those described in, for example, Japanese Patent Laid-Open Application No. 0.5 1-4 9 5 6, 2-1 7 3 0 0 7.., 2-9290 5, 2-204750-5 -11442, 5-67433, 5-11366, 6-32823, and 6-34571S polymers having a sulfonic acid group or a sulfonate group, and an azide group. Among the aforementioned water-soluble azide compounds, compounds having two or more azide groups in the molecule have particularly excellent photocrosslinkability. These compounds may be used in combination of two or more. These water-soluble azide compounds M are preferably used in an amount of 2 to 50% by weight of the copolymer. When the content of the water-soluble azide compound is less than 2% > poor sensitivity will be produced; and when the content exceeds 50¾, the physical properties of the coating film will be deteriorated > both cases are unfavorable. The photosensitive composition of the present invention can be prepared by dissolving or dispersing the aforementioned p-NVA, water-soluble azide compound, and additives depending on the application in a water-based solvent. In this case, water is generally used as a solvent, and a water-soluble solvent with a content of 50% by weight or less may be added to the water. Examples of such water-soluble solvents include methanol, ethanol, isopropanol, propane, tetrahydrofuran, dioxolane, dimethylacetamide, N-methylpyrrolidine, ethylene glycol monoethyl ether, and ethylenediamine. Alcohol monomethyl ether and propylene glycol monomethyl ether. As mentioned above, in addition to the aforementioned p-NVA and the water-soluble azide compound, the photosensitive composition of the present invention may further include a water-soluble polymer that can be crosslinked in the presence of the water-soluble azide compound. . Examples of such crosslinkable water-soluble polymers include polyvinylpyrrolidine surfaces and copolymers thereof, and selected from the group consisting of acrylamide-dipropylene-acrylamidine copolymers, poly (N, N-dimethyl paper) Standard Chengzhou China Store House Ticks (('NS) Λ4 Specification (210X 297mm) 473649 A7 B7 V. Description of the Invention (9) Allylamine), and Ν, Ν-dimethylpropenamine-acrylic acid At least one of amine copolymers.

I. A water-soluble polymer compatible with the photosensitive composition of the present invention can be added to the photosensitive composition of the present invention, and M can further improve its coatability, sensitivity, developability, and the like. However, since an excessive addition will affect the excellent physical properties of the photosensitive composition of the present invention, the amount M of the water-soluble polymer is preferably 70% by weight M of the total polymer. Examples of such a water-soluble polymer include saponified products of polyvinyl acetate, gelatin, methyl vinyl ether-maleic anhydride copolymer, vinyl alcohol-maleic acid copolymer, and water-soluble cellulose derivatives. , And polyethylene oxide. Saponification products of polyvinyl acetate which can be used in the present invention include polyvinyl alcohol and vinyl alcohol-another vinyl compound water-soluble copolymer. Examples of the saponification product of polyvinyl acetate include saponification products of polyvinyl acetate modified by a hydrophilic group, an anion, a cation, ammonium or an amidine group such as ethyl acetate. The Ministry of Economic Affairs ’s Standards Bureau sets up -1-consumption cooperatives to print water (please read the precautions on the back before filling this page). The saponified product of polyvinyl acetate M has an average polymerization of 2 0-5, 0 0 Degrees and a degree of saponification of 60-100% are better, for example. When the average degree of polymerization is less than 2000, it is difficult to obtain sufficient sensitivity; and when it exceeds 5,000, the viscosity of the light-sensitive resin is increased > It often causes disadvantageous poor coating characteristics. In addition, when the concentration K is reduced to reduce the viscosity, it is difficult to obtain a desired coating film thickness. When the degree of saponification is less than 60%, it is difficult to obtain sufficient water solubility and water developability. 1 A water-soluble copolymer of vinyl alcohol and another vinyl compound. It has an average degree of polymerization of 2000-5, 000, for example. It can be copolymerized with acetic alcohol. The paper size is suitable for China K family standard 彳 ((NS) Λ4 size (210x 297 mm) —! 〇_ 473649 A7 B7 V. Description of the invention (10) Examples include N-vinylpyrrolidone and acrylamide. Additives such as ethylene glycol, sorbitol, and

I agent * is added to the photosensitive composition of the present invention, and M improves the coatability and moisture retention property of the composition. If necessary, a silane coupling agent as an adhesion accelerator can be added to the photosensitive composition of the present invention to improve the adhesion to the substrate. Examples of usable adhesion accelerators include N-dot (aminoethyl) -aminopropylmethyldimethoxysilane and N- / S (aminoethyl-aminopropyltrimethoxysilane). If necessary, such as antiseptic Additives, defoaming agents, or pH adjusting agents are added to the photosensitive composition of the present invention. If necessary, a hydrophobic polymer emulsion can be added to the photosensitive composition of the present invention to improve film strength and water resistance. And adhesion to various substrates. Examples of hydrophobic emulsions include polyvinyl acetate emulsions, polypropylene emulsions, and urethane emulsions. In addition, colorants such as pigments or dyes can be added to the present invention. In the photosensitive composition, M prevents halo caused by exposure or produces color images. Fine-Printed in the Ministry of Agriculture and the Jujube Bureau Θ Industrial Consumer Cooperation Shirt Print $ (Please read the precautions on the back before filling this page) In particular, color images prepared by dispersing pigments in the photosensitive composition of the present invention can be applied to color filters for liquid crystal displays, color cathode ray tubes, and plasma displays; color proofs for printing; Secondary original for printing Images, etc .. The aforementioned photosensitive composition of the present invention is transparent, for example, a photosensitive composition layer is formed on a substrate by coating the photosensitive composition; pattern exposure is performed on the substrate on the photosensitive composition layer: and then The produced exposed layer is developed and processed by using water or an aqueous developer. Examples of the aforementioned substrate include the inner surface of a panel of a color cathode ray tube. This paper is a standard of Chuzhou China Storehouse Standard (('NS) Λ4) (2 丨 〇 × 297 mm), 473649 kl B7 V. Description of the invention (11) Therefore, the black matrix, phosphor pattern, color filter, etc. of the color cathode ray tube can be clearly formed.

I Next, a pattern forming method using the photosensitive composition of the present invention will be described in detail. π) Step of forming a photosensitive composition layer on a substrate There is no particular limitation on the substrate that can be used in the present invention, and any substrate to which the photosensitive composition of the present invention can adhere can be used. Examples of the aforementioned substrate include glass such as sodium alkali glass, SiO 2 treated glass, or glass coated with I το; plastic film such as polyester film, polyamide film, polyvinyl chloride film, and polypropylene film; metal Substrates; metal-laminated plastic plates and films; metal mesh; and silicon wafers. Examples of the coating method of the photosensitive composition of the present invention include spin coating, roll coating, curtain flow coating, and coater coating that are customarily used. Then, the coating layer is dried at a specific temperature by a conventional method, thereby producing a coating film. (2) Pattern Exposure Steps & 济 部 屮 ## ^^ Μ-Τ · Τ; :: Yu cooperation. ^ F (Please read the notes on the back before filling this page) You can use any conventional light source to make The coating film of the aforementioned photosensitive composition is exposed as long as it can emit light having a wavelength capable of sensitizing the water-soluble azide compound. Examples include ultra-high pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, and chemical lamps. And 5M can use any conventional exposure method, such as a reduced-projection exposure method (r e d u c t i ο -p r o j e c t ο n e x p o s u r e m t h o d), a contact exposure method, or a close exposure method. (3) Development step This paper is in Chinese standard (('NS) Λ4 size (210X 297mm) _] 4-473649 A7 B7 V. Description of the invention (I2) Available water, water-aqueous solvent Solvent mixture, or water solvents containing acids, alkalis, yuan granules, surfactants, etc., applied to the aforementioned photosensitive composition 1 (please read the precautions on the back before filling this page) by pattern irradiation Thin film development. Examples of development methods include spray development, immersion development, paddle type development, etc., which are all conventional methods. As described above, the method for forming a scheme of the present invention is applied to a color cathode The inner surface of the panel of the ray tube is particularly advantageous. Applying the aforementioned pattern forming method to the inner surface of the panel of the aforementioned color cathode ray tube can ensure high sensitivity and high resolution, thus achieving high productivity. For example, in forming color In the case of a black matrix of a cathode ray tube, graphite is coated on the aforementioned formation pattern, and the coated pattern is treated with an etchant. In this case, since the shape according to the present invention is In the case of forming a phosphor pattern, the photosensitive composition of the present invention containing a phosphor is uniformly coated on a substrate, and phosphorescence is formed thereon. Volume pattern, such as the aforementioned ocher matrix on the inner surface of the panel of a color cathode ray tube, and then drying it. The coated composition is exposed to a 1) V beam through a mask having a predetermined pattern, and then developed with water K causes only the exposed portion to remain. When red (R), green (G), and blue (B) phosphors are used, the foregoing steps are performed three times, thereby completing the phosphor surface. In the case of forming a color filter, the photosensitive composition of the present invention containing an inorganic pigment is uniformly coated on a substrate, and a color filter is formed thereon, for example, a panel of a color cathode ray tube provided with a color filter matrix And then dry it. The coated composition is exposed to UV light through a mask with a predetermined pattern. The paper is scaled to a standard of ten thresholds (('NS) Λ4 size (210X297 mm) -1 5-473649 A7 B7 V. Invention Explain (13) beam, and then develop with water, so that only the exposed part remains. When using inorganic pigments of red (R), green (G), and blue (B), the previous steps will be

I step three times, thus completing the color filter. Next, when the photosensitive composition of the present invention is used, a composition suitable for various uses will be described. First, since p-N V A used in the present invention has low oxygen permeability, an attempt was made to improve the reciprocity law failure characteristics of the photosensitive composition used to form the black matrix of a color cathode ray tube, and M achieved high resolution. Therefore, a blend of a water-soluble polymer having a high reciprocity law failure characteristic and being photo-crosslinkable in the presence of a water-soluble azide compound is preferred. As mentioned above, examples of applicable water-soluble polymers include polyvinylpyrrolidone and its copolymers, acrylamide-dipropanylpropeneamine copolymers, and poly (N, N-dimethylpropylene Fluorene), N, N-dimethyl acrylamide-acrylamide copolymer. There is no particular limitation on the blending ratio, and it is possible to choose not to increase the thickness of the coating film, but to improve the resolution of the photosensitive composition of the present invention and provide a high-sensitivity blending ratio. For example, P-N V A and another polymer may be blended at a blending ratio of K 1: 0.1 to 10. The Ministry of Economic Affairs ’Standards Bureau only works with the cooperative seal. (Please read the precautions on the back before filling out this page.) At the same time, because P-NVA has the appropriate reciprocity law failure characteristics, The photosensitive composition of the present invention does not require a special blend of a water-soluble polymer having high oxygen permeability? As mentioned earlier, a photosensitive composition having satisfactory high resolution and sensitivity can be obtained by simply dispersing a predetermined phosphor. For example, a saponified product of polyvinyl acetate or an acrylic emulsion can be used. There are no special restrictions on the phosphors used in this case, but this paper scale can be used in the Chinese standard T-mark (('NS) Λ4 specification (210X297 mm) _ · | ft _ 473649 A7 B7 V. Description of the invention (l4) Any phosphor used in a phosphor-containing display device. In the composition of the present invention, the preferred ratio of the foregoing components is P-NVA (+ (Please read the precautions on the back before filling (This page)

I another polymer): crosslinking agent: phosphor = 100: 3-30: 300-3000. When preparing the photosensitive composition of the present invention for forming a color filter, a special blend of a water-soluble polymer having high oxygen permeability is not required. And a composition type M for forming a phosphor pattern. As mentioned earlier, a photosensitive composition having satisfactory high resolution and sensitivity can be obtained by simply dispersing a predetermined inorganic pigment. However, various additives M can be used to adjust the oxygen permeability and improve the physical properties of the coating film. For example, saponification products of polyvinyl acetate and acrylic emulsions can be used. There is no particular restriction on the inorganic pigment used in this case, and any inorganic pigment used in a color filter can be used. The preferred content of the inorganic pigment is P-Η VA (+ another polymer): cross-linking agent: phosphorus precursor = 1 0 0: 3 -30: 200-2000 detailed description of the invention. The examples are described in detail, and the examples should not be construed as limiting the present invention. [Manufacturing example of P-NVA] NVA (75.76 g) and pure water (41.13 g) were placed in a 1 liter reaction equipped with a stirrer, a cooling device, a thermometer, and a nitrogen inlet. Device. Allow nitrogen to pass for 2 hours while maintaining the temperature at 54 to flush the oxygen remaining in the device, and add the monomer aqueous solution and VA-0 4 4 (0. 5 g / 4.96 g of pure water ) Azo type polymerization initiator (a product of Wako Pure Chemical Industries Ltd.) Water-soluble paper size 1 ¾ Chuanxi Pi! House Standard (rNS) M specifications (210X297 cm) ) 473649 A7 B7 V. Invention Description (15) Liquid. Then, while stirring the reaction solution, the polymerization was allowed to proceed at the same temperature for 5 hours. The residual monomer content in the polymer thus prepared was measured at G PC C analysis at 1.0% Μ. The polymer obtained had a viscosity of 2700 centipoise (25 ° C) at a polymer concentration of 7.0 weight percent and an average molecular weight of 800,000 (reduced to a starch polymer). [Example 1] A photosensitive composition having a composition shown below was prepared. 7.0 weight percent of the aforementioned polymer: 171.4 g of polyvinyl pyrrolidine (K value 90) 20 weight percent: 15.0 g (the aforementioned polymer: polyvinyl pyrrolidone = 50: 50) 4, 4'- Sodium diazidostilbene-2,2'-disulfonate (hereinafter referred to as DAS for short): 1.5 g (the aforementioned polymer solid content + vinylpyrrolidone solid content: D AS = 1 00: 1 0 ) Β Industrial Consumption Hezhushe Yinji of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Pure water: 679.9 g sand-fired coupling agent (KBM-603, Shin-Etsu Chemical Co. Ltd .): 0J 5 b

Eniulgen-810 (Kao Corporation) '0.15 g uses a 0.5 micron membrane filter to filter the photosensitive composition with the formula above, and the residual substance is applied to the inner surface of the panel of the color cathode-ray tube by spin coating and then It was dried to prepare a coating film having a thickness of 0.60 micrometers.

The paper size is 诮 州 肀 国 丨 5! House mark 埤 (('NS) Λ4 specification (210 × 297 mm) τ Q 473649 A7 B7 V. Description of the invention (16) Then there will be a pitch interval of 0.2 8 mm An orifice plate (shadow mask) is attached to the coating film, and the portions corresponding to the green, blue, and red portions of the film are exposed to the panel from a distance of 30 cm, which has a thickness of 350 nm. 15 (milliwatts per square centimeter) of light from an ultra-high pressure mercury lamp for 15 seconds. The relative humidity during the exposure was 45%. Next, the hot water was used for spray development (nozzle: Spraying System) Co.), No. 3, water pressure: 2.0 kg / cm², temperature: 40 ° C, distance 15 cm). Observation with a microscope shows that the obtained pattern faithfully corresponds to the orifice plate. Next, graphite (Hitas ο 1 6 6 S: a dispersion of Hitachi Powdered Metals Co., Ltd. is coated on the patterned panel, and the thickness of the M-graphite layer is 1.0 micron. , And fill the coated panel with 5% H J 0 + 0. 1 aqueous solution of sulfuric acid and immerse it for 60 seconds. ^ '部 十 ^ # ^^ Π-Τ7 × Negative ^ (Please read the precautions on the back before filling this page) Next, under the following conditions Spray hot water for 30 seconds: nozzle; manufactured by Spraying System Co., No. 10, water pressure of 5.0 kg / cm2, temperature: 40 t !, and distance of 15 cm. The graphite deposited thereon was removed together to obtain a matrix pattern. Microscopic observation revealed that the obtained matrix holes corresponded faithfully to the pattern. [Comparative Example 1] A photosensitive composition having the following formula was prepared. Polyethylene Pyrrolidone (K value 9 0) 2 0 weight percent: 100 g DAS: 2.0 g pure water: 567 g Paper size Chengzhou Luguo B family standard pyridine (rNS) Λ4 specification (210X 297 mm) _ 1 Q _ 473649 A7 B7 V. Description of the invention (17) Silane coupling agent (KBM-603): 0.2 g

Eniulgen-810 (Kao Corporation): 0.2 g of a photosensitive composition having a formula of M on a membrane filter of 0.5 micrometers was used to apply the liquid to the inner surface of the panel of a color cathode-ray tube by spin coating and dried Thus, a coating film having a thickness of 0.75 μm was prepared. Then, an orifice plate with a pitch of 0.28 mm was attached to the coating film, and the portions corresponding to the green, blue, and red portions of the film were exposed to a distance of 30 cm from the panel at 3 50 Ultra-high pressure mercury lamp with 0.15 (milliwatts per square centimeter) illumination at nanometers for 25 seconds. The relative humidity during the exposure was 45¾. Next, spray development was performed using hot water (nozzle: manufactured by Spray System Co., Ltd. *, water pressure 2.0 kg / cm2, temperature: 40 ° C, distance 15 cm). Next, a dispersion liquid of graphite (Hitasol 66S: a product of Hitachi Powder Metal Co., Ltd.) was coated on the aforementioned patterned panel, the thickness of the M-graphite layer was 1.0 micron, and the coated panel was filled with 5 % Η 2 0 2 + 0. 1 'Aqueous solution of sulfuric acid and soak for 60 seconds. The standard of the Ministry of Economic Affairs ^ β-τ 'Consumption Cooperative Co., Ltd. (Please read the precautions on the back before filling this page) Next, spray hot water for 30 seconds under the following conditions: nozzle; spray: manufactured by System Corporation, Ν〇. 10, water pressure 7.0 kg / cm2, temperature: 40 ° C, and distance 15 cm. Therefore, the pattern dots and the graphite deposited thereon are removed to obtain a matrix pattern. When observing the generated matrix holes, they are accompanied by edges (f r i n g e s). [Example 2]

The glass substrate on which the aforementioned ocher matrix was formed was pre-coated. U P V A This paper is standard Sichuan Chuan S House Standard ((’NS) Λ 4 size (210X 297 mm)

Product of Rhom & Haas Co.): I: 2 g 473649 A7 B7 V. Description of the invention (18) The solution is then dried. A phosphor slurry having a composition of M was applied and dried, thereby preparing a coating film having a thickness of 9 to 10 m. Then say under κ

A phosphor pattern is formed under the conditions described below. The obtained phosphor pattern exhibited high density and high resolution, and no residual phosphor was found on the ocher matrix. (Composition of phosphor slurry) Green phosphor: 100 g of a 15 X aqueous solution containing the polymer of the manufacturing example: 6 4 .3 g of 2% DAS in water-soluble: 2 5 g 10¾ EG-40 ( PV A, a product of Nippon Synthetic Chemical Industry Co., Ltd.): 45 g of inert water: 1 6 5. 7 g 5¾ Tamo 1 73 1 (Surfactant 1¾ L-62 (BASF Co.) (Please read the precautions on the back before filling out this page) After the completion of the substandard bidding, ρ, -τ elimination cooperation " imprint 9 · '1 wood (conditions for pattern formation) Orifice light source -Orifice distance from the light source: Ultra-high pressure mercury lamp illuminance exposure time on the orifice surface. Development: hot water spray development (nozzle: manufactured by Spray System Co., N cm, temperature: 40 ° C, distance 15 cm: pitch 0.8 mm: 30 cm 0. 20 mW / cm2 (called = 350 nm) 70 seconds of water pressure 2.0 kg / m2 2 1 This paper scale applies to Chinese K-house inscriptions ( ('NS) M specifications (210X 297 mm) 473649 A7 B7 V. Description of the invention (19) [Example 3] Preparation of a photosensitive composition having a formula below M ί 7.0% by weight of the aforementioned polymer: 100 g of 2,5-bis (4'-azidoy-benzylidenesulfonic acid) cyclopentane disulfonate: 1.4 g of red inorganic pigment (oxidized by iron Materials, average particle size 100 nm, Ishihara Sangyo Kaisya, Ltd.): 28 g of pure water: 350 g of silane coupling agent (KB Μ-603): 0.14 g of 5¾ Tamol 731 (surfactant, Rhom & Haas Co.'s product): 1.5 g β-τ · Consumer Cooperative Co., Ltd. Printed by the Central Bureau of Jujube of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). The photosensitive composition was coated on a sodium-alkali glass plate (10 cm x 10 cm) and dried, so that a coating film having a thickness of 1.0 micron was prepared. Then, the red component in the film was exposed to the glass plate Light of an ultra-high pressure mercury lamp with 0.20 (milliwatts per square centimeter) illuminance at 350 nm for 90 seconds. The distance between the orifice plate and the glass plate with a pitch interval of 0.8 mm is 1 cm, and The distance between the orifice plate and the lamp is 30 cm. Next, spray development using hot water (nozzle: tilting fog) Systems manufactured, square v 3, pressure 20 kg / cm2, temperature:.. 4 0 ° C, 1 5 cm distance). Microscopic observation revealed that the pattern of the obtained red pigment layer faithfully corresponds to the orifice plate. ^ This paper is in Chinese standard (州 ’NS) Λ4 size (210X 297 mm) in Shizhou China _

Claims (1)

473644i Bulletin A8 B8 C8 D8 Patent Application Scope 90. 5. 17 Revision 1. A photosensitive composition comprising a water-soluble azide compound as a photo-crosslinking agent, and a poly (N-vinyl group) which is photo-crosslinkable in the presence of a water-soluble azide compound. Acetylamine), wherein the compounding ratio of the water-soluble azide compound is 2 to 50 weight percent of the copolymer. 2. The photosensitive composition according to item 1 of the patent application scope, further comprising another water-soluble polymer that can be photocrosslinked in the presence of the aforementioned water-soluble azide compound. 3. The photosensitive composition according to item 2 of the application, wherein the other water-soluble polymer includes polyvinylpyrrolidone, acrylamide-diacetone acrylamide copolymer, poly (N, N- Dimethylacrylamide), and / or N, N-dimethylacrylamide-acrylamide copolymer. 4 · If the photosensitive composition in the scope of patent application No. 1, 2 or 3, it also contains various additives and / or water-soluble polymers. 5. A pattern forming method comprising forming a photosensitive composition layer on a substrate by coating the photosensitive composition as described in claim 1 of the scope of patent application; subjecting the substrate to pattern exposure on the photosensitive composition layer; and then The resulting exposed layer is developed using water or an aqueous developer. 6. The pattern forming method according to item 5 of the scope of patent application, wherein the photosensitive composition further comprises another water-soluble polymer that can be photo-crosslinked in the presence of the aforementioned water-soluble azide compound. 7. The pattern forming method according to item 6 of the application, wherein the other permanently soluble polymer includes polyvinylpyrrolidone, acrylamide-diacetone acrylamide copolymer 'poly (N, N- Dimethylacrylamide), and / or N, N_ dimethylacrylamide-acrylamide copolymer. This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public love) (Please read the notes on the back before filling this page) t Order I. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 473649 Α8 Β8 C8 D8 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. Application for Patent Scope 8. For the pattern formation method in the scope of Patent Application Item 5, the photosensitive composition further contains various additives and / or water-soluble polymers. 9. The pattern forming method according to any one of claims 5 to 8, wherein the substrate is an inner surface of a panel of a color cathode ray tube. 1 0 · —A photosensitive composition for forming a black matrix, the composition is used for forming a black matrix of a color cathode ray tube, and contains a water-soluble azide compound as a photo-crosslinking agent, and A photo-crosslinkable water-soluble polymer in the presence of an azide compound, wherein the photo-crosslinkable water-soluble polymer mainly comprises poly (N-vinylacetamide), and further includes a corresponding polymer (N-vinylacetamide) is another water-soluble polymer with more prominent reciprocity law failure characteristics, and the ratio of the poly (N-vinylacetamide) to another water-soluble polymer is 1: 0 1 ~ 10, and the compounding ratio of the water-soluble azide compound accounts for 2 ~ 50% by weight of the copolymer. 1 1. The photosensitive composition according to item 7 of the scope of patent application, wherein the another water-soluble polymer comprises polyvinyl pyrrolidone, acrylamide-diacetone acrylamide copolymer, poly (N, N -Dimethylacrylamide), and / or N, N_ dimethylacrylamide-acrylamide copolymer. 1 2 · A photosensitive composition for forming a phosphor pattern, wherein the composition includes a water-soluble azide compound as a photo-crosslinking agent; and a photo-crosslinkable compound in the presence of a water-soluble azide compound A water-soluble polymer; and a phosphor; and prepared by dissolving or dispersing these components in an aqueous medium, wherein the photo-crosslinkable water-soluble polymer comprises poly (N-vinylacetamide), And the aforementioned water-soluble polymer: water-soluble azide compound: phosphor is 100: 3 ~ 30: 300 ~ 3000. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) ▼ Install --------, order i * .l-- ---- si, .. 473649 A8 B8 C8 D8, patent application range 1 3, such as the photosensitive composition used to form the phosphor pattern in item 12 of the patent application range, in addition to the saponification product of polyvinyl acetate and And / or propionic acid emulsion. 1 4 · A photosensitive composition for forming a color filter, wherein the composition includes a water-soluble azide compound as a photo-crosslinking agent; a water-soluble photo-crosslinkable water-soluble azide compound in the presence of a water-soluble azide compound Polymers; and pigments; and prepared by dissolving or dispersing these components in an aqueous medium, wherein the photocrosslinkable water-soluble polymer comprises poly (N-vinylacetamide). 15. The photosensitive composition for forming a color filter according to item 14 of the scope of patent application, further comprising a saponified product of polyvinyl acetate and / or an acrylic emulsion. (Please read the note on the back before filling in this page) -Install -------- " * 打 i * -------. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Paper size applies to China National Standard (CNS) A4 (210 X 297 mm)