JP2011077251A - Member for display and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a display member free of volume-shrinkage originated defects, such as cracks and deformation, and curable at low temperature, and a method of manufacturing the same. <P>SOLUTION: The method of manufacturing a display member includes the step of curing a curable composition containing (a) polyimide having a structural unit expressed by the general formula 1 and (b) a crosslinking agent to form a patterned structure on a substrate, where R<SP>1</SP>represents quadrivalent organic, R<SP>2</SP>represents divalent organic, R<SP>4</SP>represents divalent organic, X represents divalent organic having at least one selected from carboxyl, phenolic hydroxyl, sulfonic acid and thiol, and n represents an integer of 3-200. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a display member suitable for a member such as a partition or a dielectric of a flat display such as a plasma display panel, a field emission display, and a fluorescent display tube, and a method for manufacturing the display member.

  In recent years, development of flat displays such as plasma display panels, field emission displays, fluorescent display tubes, liquid crystal display devices, electroluminescence displays, and light emitting diodes has been rapidly advanced. Among these, the plasma display generates a plasma discharge between the anode electrode and the cathode electrode facing each other in the discharge space provided between the front glass substrate and the rear glass substrate, and the gas sealed in the discharge space. Display is performed by irradiating the phosphor provided in the discharge space with the ultraviolet rays generated from the discharge. Gas discharge type displays such as plasma displays and fluorescent display tubes require partition walls for partitioning the discharge space. A field emission display such as a field emission display requires a partition for isolating the gate electrode from the cathode electrode. In the formation of a pattern structure such as a partition wall such as a plasma display or a field emission display, generally, an inorganic material such as glass powder is patterned and baked (for example, Patent Document 1). However, in this firing step, heating at about 450 to 800 ° C. is necessary, and thus there is a problem that power consumption is large and environmental load is increased. Furthermore, there is a problem that heat resistance of the substrate and other members and dimensional stability due to heat are required.

  Therefore, a technique of forming a pattern structure using an organic material, particularly a polyimide material has been developed (for example, Patent Documents 2 and 3).

JP 2002-173597 A JP 2001-28240 A JP 7-43692 A

  The above-mentioned conventionally used technique forms a pattern using a polyimide precursor that is soluble in a solvent, and then proceeds to imidization by curing at 300 to 400 ° C. Of polyimide. However, if this technology is used, it is necessary to maintain the temperature as high as 300 to 400 ° C., and volume shrinkage due to dehydration and dealcoholization reaction during imidization is large, so that a thick film such as a partition for plasma display, a high aspect ratio In the formation of the pattern, there is a problem that cracks and deformation occur.

  The present invention solves this problem and provides a high-quality display member that consumes less power in the manufacturing process. Further, the present invention provides a method for producing a display member that can be cured at a temperature of 250 ° C. or less, has a small volume shrinkage, and is less likely to cause defects.

That is, in the method for producing a display member of the present invention, (A) a polyimide having a structural unit represented by the following general formula (1) and (b) a curable composition containing a crosslinking agent is cured on a substrate. A method for producing a display member, comprising the step of forming a patterned structure on the substrate.

Furthermore, the display member of the present invention is a display member having a patterned structure on a substrate, and the patterned structure (A) is a polyimide having a structural unit represented by the general formula (1). And (B) a member for display containing a resin other than polyimide.
(Wherein R ¹ represents a tetravalent organic group, R ² represents a divalent organic group, and R ⁴ represents a divalent organic group. X represents a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a thiol group. A divalent organic group having at least one of the above groups, n represents an integer in the range of 3 to 200.)

  ADVANTAGE OF THE INVENTION According to this invention, the display member which does not have defects, such as a crack by a volume contraction, and a deformation | transformation, and can be hardened at low temperature, and its manufacturing method can be provided.

It is the schematic diagram which showed the example of the method of forming the partition of a plasma display by the thermal imprint method among the manufacturing methods of the member for display panels of this invention. It is the schematic diagram which showed the example of the method of forming the partition of a plasma display by the photolitho method thermal imprint method among the manufacturing methods of the member for display panels of this invention.

  As a result of intensive studies on a display member that can be cured at a low temperature, the inventors have found that this can be achieved by a display member and a manufacturing method as described below.

  That is, the display member of the present invention is a display member having a patterned structure on a substrate, and the patterned structure (A) is a polyimide having a structural unit represented by the following general formula (1). And (B) it is necessary to contain a resin other than polyimide.

(In the formula, R ¹ represents a tetravalent organic group, R ² represents a divalent organic group, and R ⁴ represents a divalent organic group. X represents a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. A divalent organic group having at least one selected group is shown, and n is an integer in the range of 3 to 200.)
(A) A patterned structure having high mechanical strength and good chemical resistance because the polyimide having the structural unit represented by the general formula (1) and the resin B other than (B) polyimide are uniformly compatible. And can.

  (A) Since the polyimide having the structural unit represented by the general formula (1) has good solubility in a solvent or a crosslinking agent, it can be easily handled during patterning. Moreover, since many rigid imide structures are contained, it has the characteristic that it is excellent in heat resistance and mechanical strength. The polyimide (A) preferably further has at least one group selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group not only at the terminal but also at the side chain. By having such a group at the terminal and the side chain, when an epoxy compound or an oxetane compound is used as a crosslinking agent, it can react with an epoxy group or an oxetane group, respectively, thereby forming a stronger cured film. In addition, by having such a group, solubility in an alkali developer appears in polyimide, and when a pattern is formed by photolithography using a mixture with a curable composition, an uncured portion is replaced with an alkali developer. The pattern can be easily formed.

R ¹ in the general formula (1) represents a part of the acid dianhydride residue, and may have a group selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. From the viewpoint of the solubility of the resin and reactivity with other components.

  Specific examples of the acid dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Anhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone Tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis ( 2,3-dicarboxyfe ) Methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid Anhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorenic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2- Aromatic tetracarboxylic dianhydrides such as bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanthate Examples include aliphatic tetracarboxylic dianhydrides such as carboxylic dianhydrides, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydrides, and acid dianhydrides having the structures shown below. Can do.

R ¹⁶ is an oxygen _atom, C a _{(CF 3) 2, C (} CH 3) 2, a group selected from SO ^{_2, R 17,} R ¹⁸ represents a hydrogen atom, a hydroxyl group, a group selected from a thiol ^{group, R 17} , R ¹⁸ are not simultaneously hydrogen atoms.

In the general formula (1), R ² represents a part of the residue of the diamine, and may have a group selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. And preferred from the viewpoint of reactivity with other components.

  Specific examples of diamines include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p -Phenylenediamine, 1,5-naphthalenediamine, 1,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4 -(4-aminophenoxy) phenyl} -Ter, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'- Dimethyl-4,4′-diaminobiphenyl, 3,3′-diethyl-4,4′-diaminobiphenyl, 2,2 ′, 3,3′-tetramethyl-4,4′-diaminobiphenyl, 3,3 ′ , 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene or These aromatic rings are substituted with alkyl groups or halogen atoms, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and diamines with the structures shown below. It is.

R ¹⁹ represents an oxygen atom, a group selected from C (CF ₃ ) ₂ , C (CH ₃ ) ₂ , and SO ₂ , R ²⁰ represents a group selected from a hydroxyl group and a thiol group, and R ^{21 to} R ²³ represent a hydrogen atom. Represents a group selected from a hydroxyl group and a thiol group.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be contained in R ¹ , R ² , and R ⁴ in the general formula (1) as long as the heat resistance is not lowered. preferable. Specifically, examples of the diamine component include those obtained by copolymerizing 1 to 20 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like.

  (A) The content of the polyimide having the structural unit represented by the general formula (1) is preferably 30 to 95% by weight, more preferably 35 to 90% by weight in the patterned structure. Preferably it is 50 to 70% by weight. By making content into this range, the chemical resistance of the hardened | cured material after hardening can be improved.

  The display member of the present invention contains (B) a resin other than polyimide. (B) By containing resin other than a polyimide, chemical resistance can be made favorable, and it does not elute in a solvent by a post process.

  (B) Examples of resins other than polyimide include acrylic resins, epoxy resins, oxetane resins, urethane resins, urea resins, melamine resins, phenol resins, urea resins, etc. It is particularly preferable to select from acrylic resins, epoxy resins, and oxetane resins. The chemical resistance can be further improved by selecting such a resin.

  (B) It is preferable that content of resin other than a polyimide is 5-70 weight% in a patterned structure, More preferably, it is 10-65 weight%, More preferably, it is 30-50 weight%. By making content into this range, the chemical resistance of the hardened | cured material after hardening can be improved.

  Furthermore, the display member of the present invention can be uniformly mixed without separation of (A) polyimide having the structural unit represented by the general formula (1) and (B) resin other than polyimide. is necessary. Uniformly compatible here means that different types of cross-linked polymers, or one type of cross-linked polymer and linear polymer, penetrate each other without being separated, such as an interpenetrating network structure. Refers to the state of the structure. Uniform compatibility can dramatically improve mechanical strength and chemical resistance. In a normal resin mixture that is not compatible with each other, when measured with a differential scanning calorimeter (DSC), a glass transition temperature (hereinafter referred to as Tg) is observed for each Tg of each resin alone. On the other hand, since the resins are completely integrated when they are uniformly mixed, only one new Tg is observed. Therefore, it is known that whether or not they are uniformly compatible can be determined by the number of Tg.

  In this way, the patterned structure in which different types of polymers are uniformly worn without separation contains (A) a polyimide having a structural unit represented by the following general formula (1), and (b) a crosslinking agent. It can manufacture by the process of hardening the curable composition to perform.

  As in Patent Documents 2 and 3 described above, instead of using an unclosed polyimide precursor, (A) a polyimide having a structural unit represented by the general formula (1), which is a closed ring polyimide, is used. (B) By using a low molecular weight compound called a crosslinking agent, (A) compatibility with the polyimide having the structural unit represented by the general formula (1) is improved and crosslinking is performed. It is easy to be compatible even afterwards.

  (A) Since the polyimide having the structural unit represented by the general formula (1) has good solubility in the solvent and the crosslinking agent as described above, it is easy to handle at the time of patterning. Furthermore, as described above, it is preferable to have at least one group selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group in the side chain or terminal.

  (A) The content of the polyimide having the structural unit represented by the general formula (1) is preferably 30 to 95% by weight, more preferably 35 to 90% by weight in the curable composition excluding the solvent. %, More preferably 50 to 70% by weight. By making content into this range, the chemical resistance of the hardened | cured material after hardening can be improved.

  (B) The cross-linking agent can be appropriately selected and used depending on the production method and application. For example, (b-1) an epoxy compound and / or an oxetane compound and (b-2) an ethylenically unsaturated group-containing compound are selected. One kind or a mixture of two or more kinds may be mentioned. By using these compounds, (A) compatibility with the polyimide having the structural unit represented by the general formula (1) is improved, and a cured film after curing can be easily made uniform.

  (B-1) The epoxy compound and / or oxetane compound is not particularly limited as long as it has an epoxy group or an oxetane group.

  For example, Epolite M-1230 (manufactured by Kyoeisha Chemical Co., Ltd.), NK Oligo EA-1010 / ECA (Shin Nakamura Chemical Co., Ltd.), etc. having two epoxy groups, Epolite 40E, Epolite 100E, etc. , Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 80MF, Epolite 4000, Epolite 3002 (above, manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-212L, Denacol EX-214L, Denacol EX -216L, Denacol EX-850L (above, manufactured by Nagase ChemteX Corporation), GAN, GOT (above, manufactured by Nippon Kayaku Co., Ltd.), Epicoat 828, Epicoat 1002, Epicoat 1750, Epicoat 1 07, YX8100-BH30, E1256, E4250, E4275 (manufactured by Japan Epoxy Co., Ltd.), Epicron EXA-9583, HP4032 (manufactured by Dainippon Ink & Chemicals, Inc.), VG3101 ( Mitsui Chemicals Co., Ltd.), Tepic S, Tepic G, Tepic P (above, manufactured by Nissan Chemical Industries, Ltd.), Denacol EX-321L (manufactured by Nagase ChemteX Corporation), NC6000 (Nippon Kayaku Co., Ltd.) 4) Epototo YH-434L (manufactured by Tohto Kasei Co., Ltd.), EPPN502H, NC3000 (manufactured by Nippon Kayaku Co., Ltd.), Epicron N695, HP7200 (above, Dainippon Ink & Chemicals, Inc.) ))). Two or more of these may be used in combination.

  The content of the epoxy compound and / or oxetane compound is preferably 20 to 90% by weight in total in the curable composition excluding the solvent, more preferably 35 to 80% by weight, still more preferably 40 to 70% by weight. %. By making content into this range, the mechanical strength of the hardened | cured material after hardening can be improved.

  (B-1) Among the epoxy compounds and / or oxetane compounds, examples of the oxetane compounds include etanacol EHO, etanacol OXBP, etanacol OXTP, etanacol OXMA (above, manufactured by Ube Industries, Ltd.), oxetane phenol novolak, and the like. . Two or more of these may be used in combination.

  In the present invention, the epoxy compound and / or oxetane compound preferably has two or more epoxy groups or oxetane groups. By having two or more epoxy groups or oxetane groups, a crosslinked structure can be introduced into the resin after thermosetting, and solvent resistance can be further improved. Particularly preferred is a compound represented by the general formula (3). By using these compounds, a thermosetting resin composition having very good mechanical properties after curing can be obtained.

(R ⁸ is independently selected from hydrogen or an alkyl group having 1 to 4 carbon atoms, and part or all of them may be substituted with fluorine. R ⁹ represents a divalent organic group.)
Furthermore, it is also preferable to use an epoxy compound and / or oxetane compound having a viscosity of 1 Pa · s or less as the (b-1) epoxy compound and / or oxetane compound. More preferably, it is 0.5 Pa · s or less, more preferably 0.1 Pa · s or less. By using such a compound, (A) since the polyimide having the structural unit represented by the general formula (1) can be dissolved in the epoxy compound and / or the oxetane compound, the solvent content can be reduced, and further the solvent can be reduced. A curable composition which does not substantially contain can be constituted. By reducing the solvent content, the amount of residual solvent in the cured product can be reduced, and the reliability as a display member can be improved. Furthermore, when the imprint method is used for forming the display member, it is very preferable that the curable composition does not substantially contain a solvent from the viewpoint of reducing volume change due to solvent removal during curing. Further, as described above, a compound obtained by dissolving (A) a polyimide having the structural unit represented by the general formula (1) in an epoxy compound and / or an oxetane compound has a high viscosity at room temperature and does not flow. It is also preferable for performing thermal imprinting that the viscosity is drastically reduced by being heated to ˜200 ° C. to enable deformation. The viscosity is 1 Pa. The compound which is s is shown below.

  YED-111, YED-122, YED-188, YED-205, YED-216M (above, manufactured by Japan Epoxy Resin Co., Ltd.), Epolite M-1230, Epolite EHDG-L, Epolite 40E, Epolite 100E, Epolite 200E, Examples thereof include Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF, and the like.

  Further, it is more preferable that both the epoxy compound represented by the general formula (3) and the epoxy compound having a viscosity of 1 Pa · s or less are contained. By containing both of these epoxy compounds, the chemical resistance of the cured product can be improved while reducing the amount of solvent used. The epoxy compound having a viscosity of 1 Pa · s or less is preferably 50 to 150 parts by weight, more preferably 80 to 120 parts by weight with respect to 100 parts by weight of the epoxy compound represented by the general formula (3). . By setting the content within this range, the chemical resistance of the cured product can be sufficiently improved.

  In the thermosetting resin composition of the present invention, (c) a curing accelerator can be further used. (B-1) By combining an epoxy compound and / or an oxetane compound and (c) a curing accelerator, the epoxy compound and / or the oxetane compound is cured, and the solvent resistance is improved even by heat treatment at 250 ° C. or lower. Can do. Examples of the curing accelerator include various imidazoles, imidazole silanes, imidazolines and acid anhydrides. As various imidazoles, imidazole, 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2 -Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole and the like. Examples of imidazole silane include IS-1000, IS-1000D, IM-1000, SP-1000, IA-100A, IA-100P, and IA-100F (manufactured by Nikko Materials Co., Ltd.). Examples of the acid anhydride include methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, ADEKA HARDNER EH-3326, ADEKA HARDNER EH-703, ADEKA HARDNER EH-705A (manufactured by Asahi Denka Kogyo Co., Ltd.), Epicron B-570, Epicron B-650 (above, manufactured by Dainippon Ink & Chemicals, Inc.) and the like can be mentioned. Further, a microcapsule latent curing agent is also preferably used, and specific examples include NOVACURE HX-3741, HX-3613, HX-3721, HX-3932 (above, manufactured by Asahi Kasei Corporation). . (C) Content of a hardening accelerator has the preferable range of 0.01-10 weight part with respect to a total of 100 weight part of (b-1) an epoxy compound and / or an oxetane compound. By setting it as 0.01 weight part or more, hardening of an epoxy compound and / or an oxetane compound is accelerated | stimulated effectively, and the insulation and heat resistance of hardened | cured material can be improved by setting it as 10 weight part or less.

  Furthermore, the curable composition suitably used in the present invention preferably has a viscosity η (25 ° C.) at 25 ° C. and a viscosity η (80 ° C.) at 80 ° C. in the following relationship.

η (25 ° C.) ≧ η (80 ° C.) × 50
More preferably,
η (25 ° C.) ≧ η (80 ° C.) × 100
It is. By setting the relationship between η (25 ° C.) and η (80 ° C.) within this range, the flowability of the curable composition is improved only under heating in the subsequent pattern structure forming step, and molding is easy. Become.

In order to obtain such a curable composition, (A) the epoxy compound represented by the general formula (3) 80 to 100 parts by weight of the polyimide having the structural unit represented by the general formula (1) It is preferable to use 150 to 150 parts by weight of an epoxy compound having a viscosity of 1 Pa · s or less and 150 parts by weight.
In the present invention, (b-2) an ethylenically unsaturated group-containing compound is also preferably used as the (b) crosslinking agent. These compounds are not only suitable for (A) improving the compatibility with the polyimide having the structural unit represented by the general formula (1), and obtaining a uniformly compatible cured product. d) When used in combination with a photopolymerization initiator, photolithographic processing using photopolymerization is possible. (B-2) The ethylenically unsaturated group containing compound used preferably is mentioned. Specific examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxy Ethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isode Sil acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, allylated cyclohexyl diacrylate, 1, 4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, Jito Methylolpropane tetraacrylate, glycerol diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, acrylamide, aminoethyl acrylate, phenyl acrylate , Phenoxyethyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct, diacrylate of bisphenol A-propylene oxide adduct, thiophenol acrylate, benzyl Mercaptan ak Relate, a compound in which 1 to 5 of these aromatic ring hydrogen atoms are substituted with chlorine or bromine atoms, or styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene , Brominated styrene, α-methyl styrene, chlorinated α-methyl styrene, brominated α-methyl styrene, chloromethyl styrene, hydroxymethyl styrene, carboxymethyl styrene, vinyl naphthalene, vinyl anthracene, vinyl carbazole, and the above compounds In this molecule, acrylate in the molecule is partially or entirely substituted with methacrylate, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone and the like. In the polyfunctional compound, the group having an unsaturated bond may be a mixture of an acrylic group, a methacryl group, a vinyl group, and an allyl group. In the present invention, one or more of these can be used.

  The photopolymerization initiator (d) used in the present invention is selected from those that generate radical species. (D) As a photopolymerization initiator, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 1-phenyl-1,2-propanedione-2- ( o-ethoxycarbonyl) oxime, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isop Pyrether, benzoin isobutyl ether, benzophenone and derivatives thereof, thioxanthone and derivatives thereof, acetophenone and derivatives thereof, anthraquinone and derivatives thereof, 2-hydroxy-2-methylpropiophenone, 2,4,6-trimethylbenzoylphenylphosphine oxide 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxyester, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1- ), Diphenyl sulfide derivatives, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 4-ben Yl-4-methylphenylketone, dibenzylketone, fluorenone, benzylmethoxyethyl acetal, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2 -Phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, N-phenylglycine, N-phenylthioacridone, 4 , 4-Azobisisobutyronitrile, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, benzoyl peroxide and eosin, methylene blue and other photoreductive dyes combined with reducing agents such as ascorbic acid and triethanolamine Etc. The

  In the present invention, one or more of these can be used. (D) It is preferable that a photoinitiator is added in 0.05-10 weight% with respect to the curable composition except a solvent, More preferably, it is 0.1-10 weight%. (D) If the amount of the photopolymerization initiator is too small, the photosensitivity becomes poor, and if the amount of the photopolymerization initiator is too large, the residual ratio of the exposed portion may be reduced.

  The curable composition suitably used in the present invention may contain (e) an ultraviolet absorber. By containing an ultraviolet absorber, it is possible to absorb the scattered light inside the paste due to the exposure light, increase the contrast between the exposed and unexposed areas, and easily control the degree of curing due to the height of the focal point when actinic rays are irradiated. it can. (E) Specific examples of ultraviolet absorbers include benzophenone compounds, cyanoacrylate compounds, salicylic acid compounds, benzotriazole compounds, indole compounds, inorganic fine metal oxides, and the like. Specific examples thereof include 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 2-ethyl-2-cyano-3,3-diphenyl acrylate, and BONASORB UA- which is an indole UV absorber. 3901 (manufactured by Orient Chemical Co., Ltd.), BONASORB UA-3902 (manufactured by Orient Chemical Co., Ltd.), BONASORB UA-3911 (manufactured by Orient Chemical Co., Ltd.), SOM-2-0008 (manufactured by Orient Chemical Co., Ltd.), Basic Blue, Sudan Blue, Sudan R, Examples include, but are not limited to, Sudan I, Sudan II, Sudan III, Sudan IV, Oil Orange SS, Oil Violet, Oil Yellow OB (above, Aldrich). Furthermore, a methacryl group or the like may be introduced into the skeleton of these ultraviolet absorbers and used as a reaction type. In the present invention, one or more of these can be used.

  As the (e) ultraviolet absorber in the present invention, a photo-fading compound can also be used. A photochromic compound absorbs light in the wavelength region of actinic rays when irradiated with light in the wavelength region of actinic rays and passes through changes in the chemical structure such as photodegradation and photodenaturation, and then the wavelength region of the active light source The absorbance at is lower than that before irradiation. By adding the photo-fading compound to the curable composition, it is possible to prevent the exposure light from entering the non-exposed portion, which is a portion not exposed to the exposure light in the pattern design. Specific examples of photochromic compounds include photodegradable compounds such as photochromic dyes, photoacid generators, photobase generators, and nitrone compounds, and photomodifying compounds such as azo dyes and photochromic compounds. .

  (E) It is preferable that content of a ultraviolet absorber is 0.01 to 10 weight% with respect to the curable composition except a solvent. By setting the content within this range, it is possible to sufficiently obtain the effect of improving the exposure amount margin by clarifying the photocuring contrast between the non-exposed portion and the exposed portion, and at the same time, it is possible to prevent low sensitivity. More preferably, it is 0.03 to 3 weight%.

  The curable composition suitably used in the present invention further contains (b-3) a compound having a heat-crosslinkable organic group represented by the following general formula (2). It is preferable for improving the resistance.

(In the formula, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic group having 4 to 20 carbon atoms, or an R ⁷ CO group. Also, R ⁷ has 1 to 20 carbon atoms. Represents an alkyl group of
(B-3) Examples of the compound represented by the general formula (2) include ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML as those having one of these thermally crosslinkable organic groups. -DM-BI25X- as having two, such as MC, ML-TBC (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Pa type benzoxazine (trade name, manufactured by Shikoku Chemicals Co., Ltd.) F, 46DMOC, 46DMOIPP, 46DMOEP (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X , DML-EP, DML-POP, DML-OC, dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC-Z DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nicarax MX -290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Chemicals Co., Ltd.), 2,6-dimethoxymethyl- TriML-P, TriML-35XL, TriML-TrisCR-HAP (above) and the like having 4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc. TM-BIP-A (trade) Name, manufactured by Asahi Organic Materials Co., Ltd.), TML-BP, TML-HQ, TML-p-BPF, TML-BPA, TMOM-BP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nicarak MX HML-TPPHBA, HML-TPHAP, HMOM-TPHAP (above, trade name, Honshu Chemical Industry Co., Ltd.), such as -280, Nikalac MX-270 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.) )), Nicalac MW-390, Nicalac MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.).

  Among these, in the present invention, those containing at least two thermally crosslinkable organic groups are preferable, and more preferably, Nicarax MX-280, Nicarac MX-270 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.), Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), Nikarac MW-390, Nikarac MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.) ), HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and the like.

  The curable composition obtained by adding these compounds causes the following thermal crosslinking reaction by heat during heat treatment at about 150 to 250 ° C., and further improves mechanical strength and chemical resistance.

  The addition amount of such a crosslinking agent is preferably 0.5 to 150 parts by weight, more preferably 100 parts by weight of the polyimide having the structural unit represented by the general formula (1). Is in the range of 1 to 130 parts by weight. (A) When the addition amount of (b-3) cross-linking agent with respect to 100 parts by weight of the polyimide having the structural unit represented by the general formula (1) is larger than 150 parts by weight, the resin ratio is too small. There exists a problem that heat resistance falls. On the other hand, when the amount is less than 0.5 parts by weight, there is a problem that the effect of increasing the molecular weight due to crosslinking is small and the heat resistance of the cured product is lowered.

  Furthermore, in this invention, in order to adjust the viscosity at the time of apply | coating a curable composition to a board | substrate, an organic solvent can be used. Examples of the organic solvent used here include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, 3-methoxy-3-methyl-1-butanol, Tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid and the like, and organic solvent mixtures containing one or more of these are used.

  Next, the method for producing the display member of the present invention will be described with reference to an example of a method for producing an uneven grid-like partition for a plasma display back plate, but the present invention is not limited to this.

  First, a substrate is prepared. In the present invention, since curing is sufficiently promoted at a low curing temperature, a resin substrate such as polyimide or polyethersulfone resin can be used in addition to a conventional substrate made of glass or metal. By using these resin substrates, it is possible to reduce the weight and flexibility of the display.

Next, a method for forming address electrodes on the upper surface of the substrate will be described. For example, the below-mentioned photosensitive conductive paste is applied on a substrate and dried at 60 to 100 ° C. for 5 to 30 minutes to form a coating film. Subsequently, after selectively irradiating with light through an exposure mask, development is performed to remove unnecessary portions, and heat treatment is performed at 150 to 250 ° C. to impart conductivity to form an address electrode. The composition of the photosensitive conductive paste preferably used is shown below.
(Example of photosensitive conductive paste)
Polymer: A product obtained by addition reaction of 0.8 equivalent of glycidyl methacrylate with respect to the carboxyl group of a copolymer of acrylic acid / methyl acrylate / styrene = 40/30/30% by weight (weight average molecular weight 27000, acid 100) parts by weight: Monomer: 50 parts by weight of polypropylene glycol diacrylate (manufactured by NOF Corporation, “PDP400”). Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morphol. 25 parts by weight of linophenyl) butanone-1 (manufactured by Ciba Specialty Chemicals, “IC369”), solvent: 400 parts by weight of γ-butyrolactone, conductive powder: silver flakes (manufactured by Toxen Industries, “M-13 ") 1920 parts by weight Next, a partition wall is formed. The partition can be formed by, for example, an imprint method. When using the imprint method, a step of preparing a mold having a recess corresponding to a desired partition using the curable composition, a step of filling the curable composition between the recess of the mold and the substrate, the filling The partition walls are preferably formed by a production method including a step of transferring the prepared curable composition onto the substrate. By using such a manufacturing method, an inexpensive and highly reliable partition can be provided.
(Example of curable composition-1)
Polyimide: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (0.7 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0.05 mol), 3-aminophenol (0.6 mol), 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (1.0 mol), 4 hours at 70 ° C., 3 hours at 180 ° C. 100 parts by weight of reacted polyimide (weight average molecular weight 23,000) / epoxy compound: 100 parts by weight of 1,6-hexanediol diglycidyl ether (manufactured by Japan Epoxy Resin Co., Ltd., “YED216M”), and bisphenol F type 100 parts by weight of an epoxy compound (“Epicoat 807” manufactured by Japan Epoxy Resin Co., Ltd.) and curing accelerator: imidazo 5 parts by weight of a rubber compound (“2E4MZ-A”, manufactured by Shikoku Kasei Kogyo Co., Ltd.) The curable composition of the present invention is prepared by mixing each component so as to have a predetermined composition, and then kneading three rollers or the like It can be prepared by carrying out the main kneading using an apparatus and homogeneously dispersing it. Moreover, it is also preferable to appropriately filter and degas the curable composition after the completion of the main kneading.
As described above, the curable composition thus prepared has a high viscosity at room temperature and does not flow. However, when heated, the fluidity is improved and can be deformed by pressing.

  First, the step of filling the curable composition between the concave portion of the mold and the substrate will be described. Examples of the method for filling the curable composition include a method in which the curable composition is first coated on the substrate and the mold is pressure-bonded, and a method in which the mold is filled with the curable composition and pressure-bonded to the substrate. A method for applying the curable composition on the substrate and press-bonding the mold will be described in detail below.

  The curable composition coating film of the present invention is formed on the prepared substrate with electrodes. As a formation method, it can apply | coat using methods, such as screen printing, a knife coater, a bar coater, a roll coater, a die coater, a blade coater, and can be dried as needed. In addition, it is also preferable to control the viscosity of the curable composition by heating the curable composition at the time of coating, the coating apparatus, the electrode-attached substrate, and the like to a temperature of 80 to 200 ° C. The coating thickness can be determined in consideration of the volume of the mold to be used and the film thickness under the partition pattern. Usually, it is 50-200 micrometers. The coating thickness can be adjusted by the number of coatings, the screen mesh, the viscosity of the curable composition, and the like.

  Next, a mold is pressure-bonded onto the substrate coated with the curable composition. The pressure-bonding method is not particularly limited, but if a lamination method using a vacuum press or a laminate roll is used, a uniform film free from voids and bubbles can be obtained.

  Subsequently, thermal imprinting is performed. The thermal imprint is preferably performed, for example, at 80 to 200 ° C. for 5 to 180 seconds in a state where a mold having a shape opposite to a desired partition wall is pressed onto the curable composition coating film. Moreover, in order to cool the mold temperature after shaping | molding quickly, it is also preferable to have a cooling device. After performing the thermal imprint, the mold is removed from the curable composition coating film to obtain a desired partition wall pattern. The obtained partition walls are free from defects such as deformation, cracks, and disconnection.

  Furthermore, after the curable composition is formed into a partition wall pattern, it can be heated to promote curing. The curing temperature is preferably 80 to 250 ° C. and 10 seconds to 30 minutes. In addition, this step can be omitted when the resin is sufficiently cured at the time of thermal imprinting.

  FIG. 1 schematically shows an example of a method for forming partition walls of a plasma display by the thermal imprint method using the above curable composition.

  First, as shown in FIG. 1A, a substrate 6 having a stripe-shaped address electrode 4 and a dielectric layer 5 provided on a substrate 3 is prepared, and a curable composition is heated on the substrate 6 as necessary. An object 7a is applied. Next, the mold 1 corresponding to the stepped grid-like partition is disposed, and the laminate roll 2 is used for pressure bonding, so that the curable composition 7 a is filled between the substrate 6 and the mold 1.

  Next, as shown in FIG. 1B, the mold and the substrate are heated to reduce the viscosity of the curable composition 7a, and then the mold 1 is peeled from the substrate 6 and the curable composition. Further, if necessary, thermosetting can be performed to obtain a plasma display member having the partition wall precursor 7b as shown in FIG. Subsequently, the substrate is baked at 400 to 650 [deg.] C. to obtain plasma display partition walls 7c.

As another example of the manufacturing method of the partition wall, a manufacturing method using a photolithography method will be described. When using a photolithographic method, for example, a step of applying a photosensitive curable composition as shown below onto a substrate, a step of selectively irradiating light through a mask, a step of removing a soluble portion with a developer The partition walls are preferably formed by a manufacturing method including: By using such a manufacturing method, it is possible to provide a partition wall having good uniformity over a large area and high reliability.
(Example 2 of curable composition)
Polyimide: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (0.7 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0.05 mol), Polyimide obtained by reacting 3-aminophenol (0.3 mol) and bis (3,4-dicarboxyphenyl) ether dianhydride (1.0 mol) at 70 ° C. for 4 hours and at 180 ° C. for 3 hours (weight) 100 parts by weight of an average molecular weight 25,000) / ethylenically unsaturated group-containing compound: 50 parts by weight of trimethylolpropane trimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., “TMP”) / photopolymerization initiator: 2-benzyl-2 -25 parts by weight of dimethylamino-1- (4-morpholinophenyl) butanone-1 (manufactured by Ciba Specialty Chemicals, "IC369") and solvent: 400 parts by weight of γ-butyrolactone The curable composition suitably used in the present invention is prepared using a kneading machine such as a three-roller or a rotation / revolution mixer after each component is prepared to have a predetermined composition. It can be prepared by kneading and uniformly dispersing. Moreover, it is also preferable to appropriately filter and degas the curable composition after the completion of the main kneading.

  First, the curable composition coating film of the present invention is formed on a substrate. As a formation method, it can apply | coat using methods, such as screen printing, a bar coater, a roll coater, a die coater, a blade coater, and can be dried as needed. The coating thickness can be determined in consideration of the desired partition wall height and shrinkage of the curable composition. The coating thickness can be adjusted by the number of coatings, the screen mesh, the viscosity of the curable composition, and the like. Drying is performed using a hot air drier, IR drier, etc., and the drying temperature and time can be adjusted by the solvent and coating film thickness of the curable composition used.

Next, the produced curable composition coating film is exposed. Exposure is selectively performed through a photomask. Examples of the light source used at this time include near ultraviolet rays, ultraviolet rays, electron beams, X-rays, and laser beams. Although exposure conditions vary depending on the coating thickness, exposure is usually performed for 0.01 to 30 minutes using a light source with an output of 1 to 100 mW / cm ² .

  After the exposure, development is performed by utilizing the difference in solubility between the exposed portion and the non-exposed portion in the developer. Usually, the immersion method, the spray method, the brush method, and the like are performed. As the developer, an alkaline aqueous solution is preferably used. As the alkaline aqueous solution, sodium hydroxide, sodium carbonate, potassium hydroxide aqueous solution or the like can be used. However, it is preferable to use an organic alkaline aqueous solution because an alkaline component can be easily removed during firing. As the organic alkali, a general amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, and diethanolamine. The density | concentration of aqueous alkali solution is 0.05-5 mass% normally, More preferably, it is 0.1-1 mass%. If the alkali concentration is too low, it is difficult to remove the soluble portion, and if the alkali concentration is too high, the pattern may be peeled off or corroded. The development temperature during development is preferably 20 to 50 ° C. in terms of process control.

  FIG. 2 schematically shows an example of a method for forming partition walls of a plasma display by the photolithography method using the curable composition described above.

  First, as shown in FIG. 2A, a substrate 6 having a stripe-shaped address electrode 4 and a dielectric layer 5 provided on a substrate 3 is prepared, and a curable composition 7 a is applied on the substrate 6. Next, an exposure mask for auxiliary barrier ribs is arranged, and an appropriate amount of light is irradiated at an appropriate exposure wavelength, whereby only a portion of the curable composition 7a corresponding to the auxiliary barrier ribs is cured to form barrier rib precursors 7b.

Furthermore, as shown in FIG.2 (c), curable composition 7'a is apply | coated. Next, an exposure mask for the main partition is arranged, and an appropriate amount of light is irradiated at an appropriate exposure wavelength to cure only the portion of the curable composition 7′a corresponding to the main partition as shown in FIG. Thus, a partition wall precursor 7′b is obtained.
Subsequently, development is performed to remove portions 7a and 7′a, whereby a plasma display member having partition wall precursors 7b and 7′b as shown in FIG. 1C can be obtained. Subsequently, the substrate is baked at 400 to 650 [deg.] C. to obtain plasma display partition walls 7c.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to this. By using the present invention, a 42-inch plasma display partition wall having 2.70 million pixels (1920 pixels × 1080 pixels) was manufactured.

The raw materials used for the curable composition are as follows.
Polyimide (I): 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (0.7 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0.15 Mol), 3-aminophenol (0.3 mol), bis (3,4-dicarboxyphenyl) ether dianhydride (1.0 mol) were reacted at 70 ° C. for 4 hours and at 180 ° C. for 3 hours. Polyimide (weight average molecular weight 20,000)
Polyimide (II): 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (0.057 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0.005 Mol), 3-aminophenol (0.075 mol), bis (3,4-dicarboxyphenyl) ether dianhydride (0.1 mol), reacted at 70 ° C. for 4 hours, and N, N-dimethylformamide Polyimide precursor added with dimethyl acetal (0.127 mol) (weight average molecular weight 30,000)
Crosslinking agent (I): 1,6-hexanediol diglycidyl ether (manufactured by Japan Epoxy Resin Co., Ltd., “YED216M”, viscosity 0.018 Pa.s)
Crosslinking agent (II): Bisphenol F type epoxy compound (Japan Epoxy Resin Co., Ltd., “Epicoat 807”)
Crosslinking agent (III): trimethylolpropane trimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., “TMP”)
Crosslinking agent (IV): methylol group-containing compound (Homshu Chemical Co., Ltd., HMOM-TPHAP)
Curing accelerator: 2E4MZ-A (imidazole compound, manufactured by Shikoku Chemicals Co., Ltd.)
Acrylic resin (I): A product obtained by addition reaction of 0.8 equivalent of glycidyl methacrylate to a carboxyl group of a copolymer consisting of methacrylic acid / methyl methacrylate / styrene = 40/30/30% by weight (weight average) (Molecular weight 27000, acid value 100)
(Examples 1-10, Comparative Examples 1-3)
A. Preparation of curable composition A predetermined amount of polyimide (I) and cross-linking agent (I) are weighed and stirred with a stirrer to form a uniform solution, and then a predetermined amount of cross-linking agent (II) and curing accelerator are added. It knead | mixed with this roller kneader and was set as the curable composition.
B. Preparation of partition for plasma display First, a mold is prepared. The mold corresponds to a groove corresponding to a main partition wall having a top line width (opening width) of 40 μm, a bottom line width of 20 μm and a depth of 120 μm, and an auxiliary partition wall having a top line width (opening width) of 40 μm, a bottom line width of 20 μm and a depth of 100 μm. It has a groove. The pitch of the grooves corresponding to the main partition walls was 160 μm, and the pitch of the grooves corresponding to the auxiliary partition walls was 480 μm.
A plasma display partition was produced by the following procedure. An address electrode pattern having a pitch of 160 μm and a line width of 50 μm was formed on a “PD-200” glass substrate (42 inches) manufactured by Asahi Glass Co., Ltd. by photolithography using a photosensitive conductive paste.
(Photosensitive conductive paste)
Polymer: A product obtained by adding 0.4 equivalent of glycidyl methacrylate to a carboxyl group of a copolymer of acrylic acid / methyl acrylate / styrene = 40/30/30 (weight average molecular weight 27000, acid value 100) ) 100 parts by weight Monomer: Polypropylene glycol diacrylate (manufactured by NOF Corporation, “PDP400”) 50 parts by weight Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) 25 parts by weight of butanone-1 (Ciba Specialty Chemicals, "IC369"), solvent: 400 parts by weight of γ-butyrolactone, conductive powder: silver flakes ("M-13", manufactured by Toxen Industries Co., Ltd.) Next, heat the substrate with address electrodes, the mold and the curable composition to 80 ° C. In state it was crimped mold the curable composition. In a state where the mold is pressure-bonded to the substrate via the curable composition and the electrode, the mold is peeled off from the curable composition after being held at 120 ° C. for 30 seconds, and thereafter, under the conditions described in Table 1. Curing was performed to form partition walls. Defect evaluation is AA if cracks and breaks in the obtained partition wall are within 1 place, defect evaluation is A if within 2 to 5 places, defect evaluation is B if within 6 to 20 places, partition wall in 20 or more places As a result, the defect evaluation was C.
C. Glass transition point (Tg) measurement A curable composition was applied on the entire surface of a glass substrate by screen printing and cured under the conditions shown in Table 1 to form a cured film having a thickness of 10 μm, and a differential scanning calorimeter (( Tg was measured by “DSC-50” manufactured by Shimadzu Corporation.
D. Evaluation of chemical resistance A curable composition was applied on the entire surface of a glass substrate by screen printing and cured under the conditions shown in Table 1 to form a cured film having a thickness of 10 μm. If the formed cured film is immersed in γ-butyrolactone for 30 minutes and washed with pure water, the chemical resistance is AA and the film thickness is reduced to 7-9 μm if there is no change in the coating film surface and film thickness. If a small crack of 10 μm or less occurs, the chemical resistance evaluation is A, the film thickness is reduced to 5-7 μm, or if a 10-100 μm crack is generated, the chemical resistance evaluation is B, the film thickness is The chemical resistance evaluation was C if the film was reduced to 0 to 5 μm or cracks of 100 μm or more had occurred.

Example 1
The viscosity at 25 ° C. of the curable composition prepared using the compounds shown in Table 1 is 890 Pa · s, the viscosity at 80 ° C. is 7.1 Pa · s, and η (25 ° C.) / Η (80 ° C.) is 125. Met. Further, the produced partition for plasma display had no cracks or defects, and the defect evaluation was AA. Furthermore, Tg of the produced cured film was observed only at 181 ° C., and in the chemical resistance evaluation, the film thickness was 10 μm, there was no crack, and the chemical resistance evaluation was AA.

(Example 2)
Example 1 was repeated except that no curing accelerator was added. The viscosity and Tg were almost the same as in Example 1. The produced partition for plasma display had no cracks or defects, and the defect evaluation was AA. However, in the chemical resistance evaluation, cracks of 10 μm or less occurred, so the chemical resistance evaluation was A.

(Example 3)
Example 1 was repeated except that no crosslinker (I) was added. The η (25 ° C.) / Η (80 ° C.) of the curable composition was 104. The produced partition for plasma display had no cracks or defects, and the defect evaluation was AA. However, in the chemical resistance evaluation, since a crack of 10 to 100 μm was generated, the chemical resistance evaluation was B.

Example 4
Example 1 was repeated except that polyimide (I) was dissolved in dibutyl phthalate instead of the crosslinking agent (II). The η (25 ° C.) / Η (80 ° C.) of the curable composition was 41, and the η (25 ° C.) / Η (80 ° C.) of the curable composition was 39, and the mold filling property was reduced. Thus, in the produced partition for plasma display, 12 breaks occurred, and the defect evaluation was B. However, in the chemical resistance evaluation, the film thickness was 5 μm, and the chemical resistance evaluation was B.

(Example 5)
Example 1 was repeated except that the addition amount of the crosslinking agent (I) and the crosslinking agent (II) was changed. The η (25 ° C.) / Η (80 ° C.) of the curable composition was 130. The produced plasma display partition had no defects and the defect evaluation was AA. In the chemical resistance evaluation, a crack of 10 μm or less occurred and was A.

(Example 6)
Example 1 was repeated except that the addition amount of the crosslinking agent (I) and the crosslinking agent (II) was changed. Η (25 ° C.) / Η (80 ° C.) of the curable composition was 64, and the produced partition for plasma display had four breaks, and the defect evaluation was A. On the other hand, the chemical resistance evaluation was AA.

(Example 7)
Example 1 was repeated except that the amount of polyimide (I) added was changed. Η (25 ° C.) / Η (80 ° C.) of the produced curable composition was 88. The produced partition for plasma display had four breaks, and the defect evaluation was A. When chemical resistance evaluation was performed, the crosslinking resistance was insufficient and the film thickness was 6 μm. Therefore, the chemical resistance evaluation was B.

(Example 8)
Example 1 was repeated except that the amount of polyimide (I) added was changed. The produced partition for plasma display had no defect, and the defect evaluation was AA. When chemical resistance evaluation was performed, a crack of 10 to 100 μm was generated, and the chemical resistance evaluation was B.

Example 9
Example 1 was repeated except that the curing temperature was 150 ° C. The produced partition for plasma display had no defect, and the defect evaluation was AA. When chemical resistance evaluation was performed, a crack of 10 to 100 μm was generated, and the chemical resistance evaluation was B.

(Example 10)
Example 1 was repeated except that the curing temperature was 250 ° C. The produced partition for plasma display had no defect, and the defect evaluation was AA. When the chemical resistance evaluation was performed, the evaluation was AA.

(Comparative Example 1)
Example 1 was repeated except that polyimide (II) was used as the polyimide. The shrinkage at the time of curing was large, cracks were generated in 20 or more places on the produced partition for plasma display, and the defect evaluation was C. Furthermore, imidation was insufficient at 180 ° C., and in the chemical resistance evaluation, the cured film was completely dissolved. Therefore, the chemical resistance evaluation was C.

(Comparative Example 2)
Example 1 was repeated except that the crosslinking agent (I) and the crosslinking agent (II) were not added and the polyimide was dissolved in dibutyl phthalate. Since it was not cured after imprinting and could not be peeled from the mold, the partition for plasma display could not be formed, and the defect evaluation was C. Furthermore, in the chemical resistance evaluation, since the cured film was completely dissolved, the chemical resistance evaluation was C.

(Examples 11-18, Comparative Examples 3-5)
A. Preparation of curable composition Polyimide (I), crosslinking agent (III), crosslinking agent (IV) in a predetermined amount, and a photopolymerization initiator (IC-369, manufactured by Ciba Specialty Chemicals) 25 parts by weight, As a solvent, 400 parts by weight of γ-butyrolactone was weighed and stirred with a stirrer to obtain a uniform curable composition.
B. Preparation of partition for plasma display A plasma display partition was prepared by the following procedure. An address electrode pattern having a pitch of 160 μm and a line width of 50 μm was formed on a “PD-200” glass substrate (42 inches) manufactured by Asahi Glass Co., Ltd. by photolithography using a photosensitive conductive paste.

(Photosensitive conductive paste)
Polymer: A product obtained by adding 0.4 equivalent of glycidyl methacrylate to a carboxyl group of a copolymer consisting of acrylic acid / methyl acrylate / styrene = 40/30/30% by weight (weight average molecular weight 27000, acid 100) parts by weight: Monomer: 50 parts by weight of polypropylene glycol diacrylate (manufactured by NOF Corporation, “PDP400”). Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morphol. 25 parts by weight of linophenyl) butanone-1 (manufactured by Ciba Specialty Chemicals, “IC369”), solvent: 400 parts by weight of γ-butyrolactone, conductive powder: silver flakes (manufactured by Toxen Industries, “M-13 Next, a dielectric layer is screened on the glass substrate on which the address electrodes are formed. It was formed in 20μm thickness by a printing method. Thereafter, the curable composition was uniformly applied on the back plate glass substrate on which the address electrode pattern and the dielectric layer were formed by a die coating method, and dried at 100 ° C. for 30 minutes. The thickness of the photocurable photosensitive coating film after drying was 170 μm.

Subsequently, exposure was performed by a proximity exposure machine through a negative mask having a main partition pattern having a pitch of 160 μm and a line width of 20 μm and an auxiliary partition pattern having a pitch of 480 μm and a width of 20 μm. Exposure was selected and performed in the range of 50 to 1000 mJ / cm ² depending on the curable composition.

Next, a 0.2 Wt% aqueous solution of monoethanolamine maintained at 35 ° C. was developed by applying it for 180 seconds in a shower, and was washed with water using a shower spray to remove the uncured portion. Thereafter, curing was performed under the conditions described in Table 2 to form partition walls. Defect evaluation is AA if cracks, breaks, and meandering of the partition walls are within one place, A is evaluation if within 2 to 5 places, B is defect evaluation if within 6 to 20 places, and over 20 places. Therefore, the evaluation of the defect is C.
C. Glass transition point (Tg) measurement A curable composition was applied on the entire surface of a glass substrate by screen printing and cured under the conditions shown in Table 1 to form a cured film having a thickness of 10 μm, and a differential scanning calorimeter (( Tg was measured by “DSC-50” manufactured by Shimadzu Corporation.

D. Evaluation of chemical resistance A curable composition was applied to the entire surface of a glass substrate by screen printing and cured under the conditions shown in Table 2 to form a cured film having a thickness of 10 μm. If the formed cured film is immersed in γ-butyrolactone for 30 minutes and washed with pure water, the chemical resistance is AA and the film thickness is reduced to 7-9 μm if there is no change in the coating film surface and film thickness. If a small crack of 10 μm or less occurs, the chemical resistance evaluation is A, the film thickness is reduced to 5-7 μm, or if a 10-100 μm crack is generated, the chemical resistance evaluation is B, the film thickness is The chemical resistance evaluation was C if the film was reduced to 0 to 5 μm or cracks of 100 μm or more had occurred.

(Example 11)
The partition for plasma display produced using the curable composition shown in Table 1 was free from cracks and defects, and the defect evaluation was AA. Furthermore, the Tg of the partition was only one point, and as a result of chemical resistance evaluation, the film thickness was 10 μm, no cracks, and the chemical resistance evaluation was AA. In addition, when Tg of the curable composition was measured, two points of Tg of 74 ° C. and 194 ° C. were observed, but only one point of Tg of the produced cured film was observed at 218 ° C.

(Example 12)
Example 11 was repeated except that no crosslinker (IV) was added. The produced partition for plasma display had no cracks or defects, and the defect evaluation was AA. The Tg of the prepared cured film was only one point, but the chemical resistance evaluation was B because a crack of 10 to 100 μm occurred in the chemical resistance evaluation.

(Example 13)
Example 11 was repeated except that the addition amount of the crosslinking agent (III) was changed. Since the produced partition for plasma display had insufficient crosslinking of the crosslinking agent (III), meandering occurred at two places, and the defect evaluation was A. Furthermore, Tg of the produced cured film was only one point, and as a result of chemical resistance evaluation, the film thickness was 10 μm, there were no cracks, and the chemical resistance evaluation was AA.

(Example 14)
Example 11 was repeated except that the addition amount of the crosslinking agent (III) was changed. The produced partition for plasma display had one crack, and the defect evaluation was AA. The Tg of the prepared cured film was only one point, but the film thickness was 8 μm in the chemical resistance evaluation, and the chemical resistance evaluation was A.

(Example 15)
Example 11 was repeated except that the addition amount of polyimide (I) was changed. Since the network structure of the polyimide (I) and the crosslinking agent (III) was insufficient, the produced partition for plasma display had 12 meanders, and the defect evaluation was B. On the other hand, Tg of the produced cured film was only 1 point, and chemical resistance evaluation was AA.

(Example 16)
Example 11 was repeated except that the addition amount of polyimide (I) was changed. Since the solubility of the curable composition in the developer was lowered, the produced partition for plasma display had 8 remaining films, and the defect evaluation was B. Furthermore, Tg of the produced cured film was only one point. When chemical resistance was evaluated, eight cracks were generated and the evaluation was B.

(Example 17)
Example 11 was repeated except that the curing temperature was 180 ° C. The produced partition for plasma display had no defect, and the defect evaluation was AA. The produced cured film had a Tg of only one point. When chemical resistance was evaluated, cracks of 10 μm or less occurred, and the chemical resistance evaluation was B.

(Example 18)
Example 11 was repeated except that the curing temperature was 250 ° C. The produced partition for plasma display had no defect, and the defect evaluation was AA. The Tg of the produced cured film was only one point, and when the chemical resistance evaluation was performed, the evaluation was AA.

(Comparative Example 4)
Example 11 was repeated except that a polyimide precursor was used as the polyimide. The shrinkage at the time of curing was large, cracks were generated in 20 or more places on the produced partition for plasma display, and the defect evaluation was C. The Tg of the cured film was only one point, but imidization was insufficient at 220 ° C., and in the chemical resistance evaluation, the cured film was completely dissolved, so the chemical resistance evaluation was C.

(Comparative Example 5)
Example 11 was repeated except that no crosslinker (III) was added. Since it did not have photosensitivity, the partition for plasma displays could not be formed, and the defect evaluation was C. Furthermore, although Tg of the produced cured film was only one point, in the chemical resistance evaluation, since the cured film was completely dissolved, the chemical resistance evaluation was C.

(Comparative Example 6)
Example 11 was repeated except that an acrylic resin was added instead of the crosslinking agent (III). The produced curable composition was not compatible and became cloudy. Since the curable composition was not completely uniform, the produced partition for plasma display had 20 or more disconnections, and the defect evaluation was C. Tg of the produced cured film was observed at two points. Furthermore, in the chemical resistance evaluation, since the cured film was completely dissolved, the chemical resistance evaluation was C.

DESCRIPTION OF SYMBOLS 1 Mold 2 Laminate roll 3 Substrate 4 Address electrode 5 Dielectric layer 6 Substrate 7a, 7'a Curable composition 7b, 7'b Partition precursor 7c, 7'c Partition

Claims (6)

(A) including a step of curing a curable composition containing a structural unit represented by the following general formula (1) and (b) a crosslinking agent to form a patterned structure on a substrate. The manufacturing method of the member for displays characterized by these.

(In the formula, R ¹ represents a tetravalent organic group, R ² represents a divalent organic group, and R ⁴ represents a divalent organic group. X represents a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. A divalent organic group having at least one selected group is shown, and n is an integer in the range of 3 to 200.) The method for producing a display panel member according to claim 1, wherein the step of curing the curable composition is performed at 250 ° C. or lower. 2. The crosslinking agent (b) is at least one selected from (b-1) an epoxy compound and / or an oxetane compound and (b-2) an ethylenically unsaturated group-containing compound. Or the manufacturing method of the member for a display of 2. The method for producing a display member according to claim 3, further comprising (b-3) a compound represented by the following general formula (2) as the crosslinking agent (b).

(In the formula, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic group having 4 to 20 carbon atoms, or an R ⁶ CO group. Also, R ⁶ has 1 to 20 carbon atoms. Represents an alkyl group of The method for producing a display member according to claim 1, wherein the patterned structure is a partition wall. A display member having a patterned structure on a substrate, wherein the patterned structure is (A) a polyimide having a structural unit represented by the following general formula (1), and (B) a resin other than polyimide. A display member characterized by containing.

(In the formula, R ¹ represents a tetravalent organic group, R ² represents a divalent organic group, and R ⁴ represents a divalent organic group. X represents a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. A divalent organic group having at least one selected group is shown, and n is an integer in the range of 3 to 200.)

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