• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 优先权
    • 专利摘要:
    The present invention provides a display member which is free of defects in a pattern after firing by producing a display member, in particular a plasma display member, by a manufacturing method comprising a step of applying and firing a paste containing a urethane compound and inorganic fine particles on a substrate. will be.
    公开号:KR20010107615A
    申请号:KR1020010027899
    申请日:2001-05-22
    公开日:2001-12-07
    发明作者:히로꼬 우에가끼；노리까즈 다바따；다까끼 마사끼；히로미쓰 다까하시；아끼히꼬 다나까；미쓰요 하시모또
    申请人:히라이 가쯔히꼬；도레이 가부시끼가이샤；
    IPC主号:
    专利说明:

    Paste, Display Member and Method for Manufacturing the Display Member}
    [1] The present invention relates to a method for producing a paste and a display member using the same. The paste and manufacturing method of this invention can be used for manufacture of various displays, including a plasma display, a plasma address liquid crystal display, a field emission display, and pattern processing of circuit materials.
    [2] Recently, miniaturization and high precision of circuit materials and displays have been progressed, and a pattern processing technology capable of coping with this has been demanded. In particular, in forming the partition wall of a plasma display, the method which can pattern-process an inorganic material, such as glass, with a high precision and high aspect ratio is calculated | required.
    [3] Conventionally, as a method of patterning an inorganic material, Japanese Patent Laid-Open No. 9-310030 and US Patent 6197480 propose a method of forming a pattern by photolithography using a photosensitive paste.
    [4] However, the above method has a problem that when the organic component is removed by firing, the plastic shrinkage force due to the crosslinking of the organic component acts, and defects such as peeling and disconnection tend to occur in the pattern. Therefore, the present inventors earnestly examined and completed this invention in order to provide the paste in which defects, such as peeling and disconnection, do not generate | occur | produce at the time of baking.
    [5] That is, the present invention relates to a paste containing a urethane compound and inorganic fine particles.
    [6] Moreover, this invention relates to the paste of Claim 1 whose weight at the time of heating up to 500 degreeC and 100 degreeC as a paste containing inorganic fine particle and an organic component is represented by following Formula.
    [7] (Weight at 500 ° C) / (weight at 1000 ° C) ≤1.05
    [8] In addition, the present invention is a paste containing inorganic fine particles and organic components, the average film stress calculated from the amount of warpage of the silicon wafer due to shrinkage of the thin film when the paste is applied on the silicon wafer to form a thin film and heated up to 500 ° C. It relates to a paste having a maximum value of 0.1 to 20 MPa.
    [9] Moreover, this invention relates to the manufacturing method of the display member containing the process of apply | coating and baking the paste containing a urethane compound and an inorganic fine particle on a board | substrate.
    [10] The invention also relates to a method of manufacturing a display, in particular a plasma display, using the same.
    [11] The paste of the present invention contains an organic component and inorganic fine particles. In the present invention, the organic component excludes inorganic fine particles from the paste. The paste of this invention can be used for the purpose of forming a pattern which consists of inorganic substance by baking after forming a pattern by various methods and removing an organic component.
    [12] The pattern which consists of substantially an inorganic substance manufactured using the paste of this invention can be used suitably as a partition of a plasma display panel back plate in a display use, especially a plasma display use.
    [13] In addition to the urethane compound and the inorganic fine particles, a binder polymer, a dispersant, a plasticizer, a thickener, an organic solvent, an antisettling agent, an antioxidant, and the like can be added to the paste used in the present invention as necessary.
    [14] It is preferable that the molecular weight of the urethane compound used by this invention is 15000-50000. In addition, molecular weight here means a weight average molecular weight. By setting it as 15000 or more, the flexibility of a urethane can be maintained and defects, such as peeling of a pattern and disconnection at the time of baking, can be reduced further. By setting it as 50000 or less, the viscosity of a urethane can be reduced and handling can be made easy.
    [15] As a urethane compound used by this invention, the compound represented by following formula (1) is mentioned, for example.
    [16] R 1- (R 4 -R 3 ) n -R 4 -R 2
    [17] Here, R 1 and R 2 are selected from the group consisting of a substituent including an ethylenically unsaturated group, hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and a hydroxyaralkyl group, and may be the same or different. R 3 is an alkylene oxide group or an alkylene oxide oligomer, and R 4 is an organic group containing a urethane bond. n is a natural number of 1-10.
    [18] It is preferable that a urethane compound contains the ethylene oxide unit. More preferably, in formula (1), R <3> is an oligomer containing an ethylene oxide unit and a propylene oxide unit, and the ethylene oxide unit content in the said oligomer exists in the range of 8 to 70 weight%. When the ethylene oxide unit content is 70% by weight or less, the flexibility can be improved and the stress at the time of forming the partition wall can be reduced, so that defects such as disconnection of the partition wall can be effectively suppressed. Moreover, thermal decomposition property improves and a baking residue becomes hard to generate | occur | produce in the baking process after formation of a partition. Moreover, compatibility with another organic component improves because ethylene oxide unit content is 8% or more. The compatibility of an organic component can be measured by the haze of the coating film which apply | coated and formed the organic component. The small haze indicates that the organic components are compatible with each other. It is preferable that haze becomes 5.0% or less in the coating film of 30 micrometers in thickness. Here, the haze (H: unit%) is measured by the diffusion light transmittance (Td) and the total light transmittance (Tt) by using an integrated sphere light transmittance measuring device according to JIS K7105 "Plastic Optical Property Test Method". It is calculated by obtaining = (Td / Tt) × 100). Haze becomes like this. More preferably, it is 0.8% or less, More preferably, it is 0.5% or less.
    [19] It is preferable that the organic group containing the urethane bond of R <4> is produced by condensation of a diisocyanate group and a hydroxyl group. As a component which has a diisocyanate group used here, aromatic diisocyanate compounds, such as 1, 4- diisocyanate butane and 1.6- diisocyanate hexane, 1, 4- phenylene diisocyanate, toluylene diisocyanate, or 1 Alicyclic diisocyanate compounds, such as a 4-cyclohexylene diisocyanate and an isophorone diisocyanate, can be used. It is more preferable to use an alicyclic isocyanate compound and it is especially preferable to use isophorone diisocyanate, but it is not limited to this.
    [20] Specific examples of the urethane compound used in the present invention include UA-2235 PE (molecular weight 18000, EO content 20%), UA-3238 PE (molecular weight 19000, EO content 10%), UA-3348 PE (molecular weight 22000, EO content 15 %), UA-2349 PE (molecular weight 27000, EO content 7%), UA-5348 PE (molecular weight 39000, EO content 23%) (above, manufactured by Shin-Nakamura Kagaku Co., Ltd.), and the like, but are not limited thereto. It doesn't happen. In addition, these compounds can be mixed and used.
    [21] It is preferable that content of a urethane compound is 0.1-20 weight% in a paste. By making content into 0.1 weight% or more, the effect of suppressing peeling appropriately can be acquired. When it exceeds 20 weight%, the dispersibility of an organic component and inorganic fine particles falls and it is easy to produce a defect.
    [22] The paste used in the present invention is also a photosensitive paste by adding reactive monomers, reactive oligomers, reactive polymers, photopolymerization initiators, photoacid generators, photobase generators, sensitizers, sensitizers, ultraviolet absorbers, organic dyes, acids, bases, and the like. Can be used as Here, the reactivity in the reactive monomer, the reactive oligomer and the reactive polymer means that when the paste is irradiated with active light, the reactive monomer, the reactive oligomer or the reactive polymer causes a reaction such as photocrosslinking, photopolymerization, photodepolymerization, photomodification, or the like. It means that the chemical structure changes. In this case, the display member can be manufactured by photolithography.
    [23] The reactive monomer, the reactive oligomer and the reactive polymer preferably have ethylenically unsaturated bonds. It is also preferable that the ethylenically unsaturated bond concentration in the paste is 0.2 to 1.0 mol per kg of paste before active light irradiation. By setting the ethylenically unsaturated bond concentration in the paste to 0.2 mol or more, the paste sensitivity can be maintained and good pattern formation property can be obtained. By setting the ethylenically unsaturated bond concentration to 1.0 mol or less, the crosslinking density at the time of pattern formation is maintained in an appropriate range and the binder removal property is improved. In addition, polymerization shrinkage due to light or heat is suppressed, and defects such as peeling and disconnection are less likely to occur.
    [24] As the reactive monomer, the paste of the present invention preferably further contains an amine compound having an ethylenically unsaturated group. It is particularly preferable to contain at least one of the amine compounds represented by the following general formula (3) or (4) because the sensitivity to light may be improved.
    [25] R 5 R 6 R 7 N
    [26] R 5 R 6 NM-NR 7 R 8
    [27] Here, R 5 is a substituent containing an ethylenically unsaturated group, R 6 , R 7 , R 8 is a substituent containing an ethylenically unsaturated group, hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group and a hydroxyalkyl group One selected from the group consisting of, R 6 , R 7 , R 8 may be the same or different. M represents a divalent linking group.
    [28] As a substituent R 5 containing the ethylenically unsaturated group of an amine compound, what is represented by either of following formula (5), (6) or (7) is preferable.
    [29] CH 2 = CR 9 -A- (L) a -CH (OH) -CH 2-
    [30] CH 2 = CR 9- (A) b- (L) a -SO 2-
    [31] CH 2 = CR 9- (A) b- (L) a -CO-
    [32] Here, R 9 is hydrogen or methyl group, A is COO, CONH or substituted or unsubstituted phenylene group, L is selected from cyclic or acyclic alkylene, allylene and aralkylene groups having 1 to 20 carbon atoms. L may be unsubstituted and may be further substituted with an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, an aryl group, or the like. And a and b are O or 1;
    [33] More preferably, CH 2 = C (CH 3 ) COOCH 2 CH (OH) CH 2 −.
    [34] Moreover, it is preferable to use a tertiary amine compound as an amine compound, and the compound which has a structure especially represented by following formula (8) is used preferably.
    [35] (CH 2 = CR 10 -CO-Z) 8-m -NR ' m
    [36] Wherein R 10 is a hydrogen atom or a methyl group, R 'is an alkyl group, an aryl group, an aralkyl group or a hydroxyalkyl group, Z is -OR "-or -NHR"-, R "is an alkylene group, an arylene group, an aralkylene group or It is a hydroxyalkylene group, m is 0, 1 or 2.
    [37] The most preferred amine compound for use in the present invention is bis (2-hydroxy-3-methacryloyloxypropyl) isopropylamine.
    [38] Preparation of an amine compound having an ethylenically unsaturated bond is an amino compound containing glycidyl acrylate, glycidyl methacrylate, acrylic acid chloride, methacrylic acid chloride, acrylic anhydride, methacrylic anhydride and the like having an ethylenically unsaturated bond. React with A plurality of ethylenically unsaturated group containing compounds can be mixed and used. Although the above compound is mentioned as an amine compound which has an ethylenically unsaturated bond, It is not limited to these. In addition, these compounds can be mixed and used.
    [39] In this invention, the reactive monomer which has ethylenically unsaturated bond other than the said amine compound can be used as needed. As such a reactive monomer, the monomer etc. which have 1 or more photopolymerizable acrylate group, a methacrylate group, or an allyl group are mentioned. Specific examples thereof include acrylic acid or methacrylic acid esters of alcohols (for example, ethanol, propanol, hexanol, octanol, cyclohexanol, glycerin, trimethylolpropane, pentaerythritol, etc.), carboxylic acids (for example acetic acid). , Propionic acid, benzoic acid, acrylic acid, methacrylic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, citric acid and the like) and glycidyl acrylate, glycidyl methacrylate, allyl glycidyl or tetraglycidyl methacrylylenediamine And reaction products, amide derivatives (for example, acrylamide, methacrylamide, N-methylolacrylamide, methylenebisacrylamide, and the like), and reactants of epoxy compounds with acrylic acid or methacrylic acid. In the polyfunctional monomer, the unsaturated group may be present by mixing acryl, methacryl, vinyl and allyl groups. These may be used alone or in combination.
    [40] Moreover, as a reactive oligomer, it is preferable that a urethane compound has ethylenically unsaturated group. Since the ethylenically unsaturated group of a urethane compound reacts with ethylenically unsaturated groups, such as a reactive monomer and a reactive polymer, and is contained in a crosslinked material, polymerization shrinkage can also be suppressed.
    [41] The paste of the present invention may contain a copolymer polymer having a carboxyl group.
    [42] Examples of the copolymer having a carboxyl group include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinylacetic acid, or acid anhydrides thereof, and methacrylic acid esters, acrylic acid esters, styrene and acrylics. It can obtain by selecting monomers, such as ronitrile, vinyl acetate, and 2-hydroxyacrylate, and copolymerizing using an initiator like azobisisobutyronitrile.
    [43] As a copolymer which has a carboxyl group, since the thermal decomposition temperature at the time of baking is low, the copolymer which uses acrylic acid ester or methacrylic acid ester, and acrylic acid or methacrylic acid as a copolymerization component is used preferably. In particular, a styrene / methyl methacrylate / methacrylic acid copolymer is preferably used.
    [44] It is preferable that the acid value of the copolymer which has a carboxyl group is 50-150 mgKOH / g. By allowing the acid value to be 150 mgKOH / g or less, the developing tolerance can be widened. Moreover, the solubility with respect to the developing solution of an unexposed part does not fall by setting an acid value to 50 mgKOH / g or more. Therefore, it is not necessary to increase the developer concentration, and it is possible to prevent exfoliation of the exposed portion and to obtain a high precision pattern.
    [45] Moreover, it is also preferable that the copolymer which has a carboxyl group has an ethylenically unsaturated group in a side chain. As an ethylenically unsaturated group, an acryl group, methacryl group, a vinyl group, an allyl group, etc. are mentioned.
    [46] The method of adding such side chains to the copolymer is made by addition reaction of an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride to a mercapto group, an amino group, a hydroxyl group or a carboxyl group in the copolymer. There is a way.
    [47] As an ethylenically unsaturated compound which has a glycidyl group, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, ethyl acrylate glycidyl, crotonyl glycidyl ether, crotonic acid glycidyl ether, isocrotone Shanglycidyl ether etc. are mentioned. Examples of the ethylenically unsaturated compound having an isocyanate group include acryloyl isocyanate, methacryloyl isocyanate, acryloylethyl isocyanate, methacryloylethyl isocyanate and the like. The ethylenically unsaturated compound having an glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride is preferably added in an amount of 0.05 to 1 molar equivalent to the mercapto group, amino group, hydroxyl group or carboxyl group in the polymer.
    [48] In order to obtain a suitable exposure amount, it is preferable that the addition amount of the copolymer which has a carboxyl group is 10 to 90 weight% in the organic component except a solvent.
    [49] When the binder component is required, polyvinyl alcohol, polyvinyl butyral, methacrylic acid ester polymer, acrylic acid ester polymer, acrylic acid ester-methacrylic acid ester copolymer, butyl methacrylate resin and the like can be used.
    [50] The photoinitiator which can be used for this invention is selected and used from what generate | occur | produces a radical species. As a photoinitiator, diethoxy acetophenone, 2-hydroxy-2- methyl-1- phenyl propane- 1-one, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2- methyl propane- 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 isopropyl ether, benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone , 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, alkylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycar Bonyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromine De, (4-benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzophenoxy) -N, N, N-trimethyl-1-propenealuminum chloride- hydrochloride, 2-isopropyl Thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo- 9H-Tioxanthen-2-yloxy) -N, N, N-trimethyl-1-propananium chloride, 2,4,6-trimethylbenzoylphenylphosphine oxide, 2,2'-bis (o- Chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrene Quinone, camphorquinone, methylphenylglyoxyester, η 5 -cyclopentadienyl-η 6 -cumenyl-iron (1 +)-hexafluorophosphate (l-), diphenylsulfide derivative, bis (η 5- 2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (lH-pyrrol-1-yl) -phenyl) titanium, 4,4-bis (dimethylamino) benzophenone , 4,4-bis (diethylamino) Zophenone, thioxanthone, 2-methyl thioxanthone, 2-chlorothioxanthone, 4-benzoyl-4-methylphenyl ketone, dibenzyl ketone, fluorenone, 2,3-diethoxyacetophenone, 2,2- Dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, benzylmethoxyethylacetal, anthraquinone, 2-t-butylanthraquinone, 2 Aminoanthraquinone, β-chloranthhraquinone, antron, benzanthrone, dibenzsvelon, methyleneanthrone, 4-azidebenzalacetphenone, 2,6-bis (p-azidebenzylidene) cyclohexane , 2,6-bis (p-azidebenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadione-2- (o-methoxycarbonyl) oxime, 1,3-di Phenylpropanetrione-2- (o-ethoxycarbonyl) oxime, naphthalenesulfonylchloride, quinolinesulfonylchloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, benzthiazol disulfide Feed, triphenylphosphine, carbon tetrabromide, And combinations of photoreducing pigments such as tribromophenyl sulfone, benzoyl peroxide and eosin, methylene blue, and reducing agents such as ascorbic acid and triethanolamine.
    [51] In the present invention, these may be used alone or in combination of two or more. The photopolymerization initiator is preferably added in the range of 0.05 to 10% by weight with respect to the organic component, more preferably 0.1 to 10% by weight. By making the addition amount of a photoinitiator into this range, favorable photosensitivity can be obtained, maintaining the residual ratio of an exposure part.
    [52] A sensitizer can be used together with a photoinitiator to improve the sensitivity or to extend the wavelength range effective for the reaction. Specific examples of the sensitizer include 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-isopropyl thioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2 , 6-bis (4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (diethylamino) benzo Phenone, 4,4-bis (dimethylamino) carcon, 4,4-bis (diethylamino) carcon, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p -Dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4-dimethylaminophenylvinylene) isonnaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carr Bonylbis (4-diethylaminobenzal) acetone, 3,3-carbonylbis (7-diethylaminocoumalin), triethanolamine, methyldiethanolamine, triisopropanolamine, N-phenyl-N-ethylethanolamine , N-phenylethanolamine, N-tolyl diethan Amine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl dimethylaminobenzoic acid, isoamyl diethylaminobenzoic acid, benzoic acid (2-dimethylamino) ethyl, 4-dimethylaminobenzoic acid (n-butoxy ) Ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthio tetrazole, etc. are mentioned.
    [53] In the present invention, these may be used alone or in combination of two or more. Moreover, some sensitizers can be used also as a photoinitiator. When a sensitizer is added to the paste of the present invention, the amount added is preferably 0.05 to 10% by weight, more preferably 0.1 to 10% by weight based on the organic component. By making the addition amount of a sensitizer into this range, favorable photosensitivity can be obtained, maintaining the residual ratio of an exposure part.
    [54] In this invention, antioxidant is added preferably. Antioxidants have radical chain inhibitory action, triple scavenging action, and hydroperoxide decomposition.
    [55] The paste contains many glass fine particles, for example, when used for the manufacture of partition walls of plasma display members. Therefore, light scattering in the paste due to the exposure light is difficult to avoid, and the thickening of the partition pattern shape and the depression between the patterns (that is, residual film formation) that are considered to be caused by it are likely to occur. It is preferable that the walls of the partition pattern are vertically erected and become spherical. Ideally, the exposed paste coating film dissolves in the developer at a certain exposure amount or less, and becomes insoluble in the developer at or above the exposure amount. In other words, even if the coating film is exposed at a low exposure amount due to light scattering, it is preferable to dissolve it in the developer so that even if the exposure amount is increased, the thickness of the pattern shape and the depression between the patterns are less likely to occur, and the range that can be developed becomes wider.
    [56] Addition of an antioxidant to the paste causes the antioxidant to trap radicals or return the energy state of the excited photopolymerization initiator or sensitizer to the ground state, thereby suppressing the extra photoreaction caused by the scattered light and preventing it from being inhibited by the antioxidant. By rapidly causing the photoreaction, the contrast of dissolution and insoluble in the developer can be increased.
    [57] Specific examples of the antioxidant include p-benzoquinone, naphthoquinone, p-xyloquinone, p-tolquinone, 2,6-dichloroquinone, 2,5-diacetoxy-p-benzoquinone, 2,5 Dicaproxy-p-benzoquinone, hydroquinone, pt-butylcatechol, 2,5-dibutylhydroquinone, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, di-t-butyl- p-cresol, hydroquinone monomethyl ether, α-naphthol, hydrazine hydrochloride, trimethylbenzylammonium chloride, trimethylbenzylammonium oxalate, phenyl-β-naphthylamine, parabenzylaminophenol, di-β-naphthylparaphenylenediamine , Dinitrobenzene, trinitrobenzene, picric acid, quinone dioxime, cyclohexanone oxime, pyrogarol, tannic acid, triethylamine hydrochloride, dimethylaniline hydrochloride, couron, (2,2'-thiobis (4-t- Octylphenolate) -2-ethylhexylaminonickel- (II), 4,4'-thiobis- (3-methyl-6-t-butylphenol), 2,2'-methylenebis- (4-methyl- 6-t-butylfe Knoll), 2,2'-thiobis- (4-methyl-6-t-butylphenol), triethylene glycol-bis [3- (t-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1,6-hexanediol-bis [(3.5-di-t-butyl-4-hydroxyphenyl) propionate], 1,2,3-trihydroxybenzene, and the like, but are not limited thereto. In the present invention, one or more of these may be used.
    [58] The amount of the antioxidant added is preferably in the range of 0.1 to 30% by weight, more preferably 0.5 to 20% in the paste. By carrying out the addition amount of antioxidant in this range, the contrast of melt | dissolution and insoluble in a developing solution can be enlarged, maintaining the light sensitivity of a paste, maintaining a degree of polymerization, and maintaining a pattern shape.
    [59] In addition, by adding an ultraviolet absorber to the paste, the scattered light in the paste due to the exposure light can be absorbed and the scattered light can be weakened. Examples of the ultraviolet absorbents include benzophenone compounds, cyanoacrylate compounds, salicylic acid compounds, benzotriazole compounds, indole compounds, and inorganic fine metal oxides. Among these, a benzophenone type compound, a cyanoacrylate type compound, a benzotriazole type compound, or an indole type compound is especially effective. As specific examples of these, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydrate Hydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzo Phenone, 2-hydroxy-4-methoxy-5-sulfobenzophenonetrihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2, 2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone , 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2' -Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro Benzotriazole, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzotriazole, 2-ethyl Sil-2-cyano-3,3-diphenylacrylate, 2-ethyl-2-cyano-3,3-diphenylacrylate, "BONASORB" which is an indole absorbent UA-3901 (Orient Chemical Industries, Ltd.) Manufacture), "BONASORB" UA-3902 (made by Orient Kagaku Co., Ltd.), SOM-2-0008 (made by Orient Kagaku Co., Ltd.), etc., Although it is not limited to these. In addition, a methacrylic group etc. can be introduce | transduced into the skeleton of these ultraviolet absorbers, and can be used as a reaction type. In the present invention, one or more thereof can be used.
    [60] The amount of the ultraviolet absorber added is preferably in the range of 0.001 to 10% by weight, more preferably 0.5 to 5% in the paste. By setting it in this range, the transmission limit wavelength and wavelength gradient width may be in a desired range, and the absorption effect of scattered light can be acquired, maintaining the transmittance | permeability of exposure light and the sensitivity of a paste.
    [61] In the present invention, an organic dye can be added to the paste as an indication of exposure and development. By adding and coloring the dye, the visual perception is improved, and it becomes easy to distinguish between the portion where the paste remains and the removed portion during development. Although it does not specifically limit as organic dye, It is preferable that it does not remain in the insulating film after baking. Specifically, anthraquinone dyes, indigoide dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes and naphthoquies. Non-base dyes, phthalimide dyes, pelinone dyes and the like can be used. In particular, when absorbing light of wavelengths near the h-line and i-line, for example, a carbon-based dye such as basic blue, the effect of the present invention is more likely to appear, which is preferable. The amount of the organic dye added is preferably 0.001 to 1% by weight.
    [62] An organic solvent is used in order to adjust the viscosity at the time of apply | coating a paste to a board | substrate according to a coating method. The organic solvent used at this time is methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran , Dimethyl sulfoxide, γ-butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, and the like, and an organic solvent mixture containing one or more of them is used.
    [63] It is preferable that the paste of this invention is 40 weight%-80 weight% of the inorganic fine particle in a paste. Too many organic components increases the amount of material that must be removed in the firing process, resulting in long firing times and difficult complete mineralization. In addition, since the plastic shrinkage rate is increased, there is a problem in terms of pattern formation, such as the need to thicken the coating film in order to form a partition having a desired size. It is also unpreferable also in the maintenance surface of a partition shape. If the organic component is too small, not only the mixing and dispersion of the inorganic fine particles in the paste will be insufficient, but also the problems such as a decrease in the applicability of the paste due to the increase in the viscosity of the paste will adversely affect the stability of the paste. There is a thing. Moreover, since the dispersibility of an organic component and an inorganic fine particle falls, defects arise easily at the time of baking.
    [64] It is preferable that an inorganic fine particle consists of 60 to 97 weight% of low melting glass powders, and 3 to 40 weight% of fillers of 1-4 micrometers of average particle diameters. The filler is used together with the low melting glass in order to control the plastic shrinkage rate and to maintain the strength of the formed partition wall. The addition effect is less than 3 weight%, and when it exceeds 40 weight%, since the problem, such as a decrease of the strength of a partition, arises, it is unpreferable.
    [65] The inorganic fine particles may also contain up to 30% by weight of oxide fine particles having an average particle diameter of 0.003 to 0.02 µm.
    [66] Moreover, it is preferable that the refractive index of the low melting glass powder and the filler is 1.45-1.65. The paste is obtained by dispersing inorganic fine particles in an organic solvent system in which an organic component is dissolved. In the coating film, the inorganic fine particles are present in a considerably high concentration in the organic component layer. It is preferable to approximate the refractive index of each component in a paste in order to pattern-form to such a coating film by the photolithographic method. Since the average refractive index of the organic component to be used is usually in the range of 1.4 to 1.7, it is preferable to select one that is as close as possible to the refractive index of the inorganic fine particles. The glass component which consists of various oxides can control a characteristic by considering the compounding, and also the low melting glass powder which controlled the thermal characteristic, refractive index, etc. can also be used also in this invention. As low-melting-point glass powder, it is preferable that refractive index is 1.45-1.65, glass transition point is 400-550 degreeC, and load softening point is 450-600 degreeC. By setting the load softening point to 450 ° C. or higher, the partition wall does not deform in the subsequent steps of member formation and display formation. The load softening point is 60 ° C. or lower to melt during firing to obtain a high strength partition wall.
    [67] The low-melting-point glass powder used for the paste has good filling and dispersibility at the time of forming the paste, and has an average particle diameter of 1 to 4 µm in order to enable application at a uniform thickness of the paste and to maintain good pattern formability. It is preferable that the largest particle diameter is 35 micrometers or less. Although glass powder having such a particle size distribution is excellent in terms of filling into a paste and dispersibility, a powder having a considerably large particle size is also acceptable in the case of low melting glass powder because most of it is melted and integrated in the firing process. If it is this range, it can satisfy | fill filling property and dispersibility, and can comprise the paste excellent in applicability | paintability and pattern formation property.
    [68] As the filler of the present invention, at least one selected from high melting point glass and cordierite having a refractive index adjusted is preferably used. As high melting point glass powder, what has glass transition point 500-1200 degreeC and load softening point 550-1200 degreeC is preferable.
    [69] The paste of the present invention can be used as a conductive paste by using metal fine particles as inorganic fine particles. By using this conductive paste, a circuit pattern with high precision and few defects can be obtained. This conductive paste can be used, for example, for forming electrodes of plasma displays.
    [70] As the metal fine particles, noble metal conductive fine particles such as Au, Ni, Ag, Pd, and Pt are preferable. Each may be used alone or as a mixed powder. It is preferable to add Cr or Rh to these in that high temperature characteristics can be improved.
    [71] When used with the photosensitive paste, the average particle diameter of these metal fine particles is preferably 0.5 to 5 m. When the average particle diameter is less than 0.5 µm, light rays do not penetrate smoothly through the inside of the film after application during ultraviolet exposure, and it becomes difficult to form a fine pattern having a line width of 60 µm or less of the good conductor. On the other hand, when the average particle diameter exceeds 5 mu m, the unevenness of the surface of the circuit pattern after the application becomes rough, the pattern accuracy is lowered and causes noise. The metal fine particles preferably have a specific surface area of 0.1 to 3 m 2 / g. When the specific surface area is less than 0.1 m 2 / g, the accuracy of the circuit pattern is lowered. Moreover, if it exceeds 3 m 2 / g, the surface area of the powder is too large, ultraviolet light is scattered and the pattern precision is lowered.
    [72] As the shape of the metal fine particles, a flake (plate, cone, rod) or spherical shape can be used. Since aggregation is suppressed and there is little scattering of ultraviolet light at the time of exposure, it is preferable that it is spherical.
    [73] It is preferable to heat up the paste of this invention to 500 degreeC and 1000 degreeC on the conditions of 10 degree-C / min, and the weight measured by the thermogravimetric apparatus is represented by following Formula.
    [74] (Weight at 500 ° C) / (weight at 1000 ° C) ≤1.05
    [75] The small weight ratio in 500 degreeC and 1000 degreeC shows that the binder removal property of an organic component is favorable. If the said ratio is 1.05 or less, residual organic components in a partition can be reduced and the reliability of a display can be improved. By adding a urethane compound in a paste, the said weight ratio can be made small. In particular, when the ethylene oxide unit content in a urethane compound exists in the said range, a weight ratio can be made smaller and it is preferable. Moreover, when a paste contains the compound containing an ethylenically unsaturated group, the said weight ratio can be controlled by controlling an ethylenically unsaturated bond concentration.
    [76] When the paste of the present invention was applied on a silicon wafer to form a thin film of 3 to 10 μm and heated up from 30 ° C. to 500 ° C. in 1 hour, the amount of warpage of the silicon wafer due to shrinkage of the thin film was calculated using the following equation. It is preferable that the maximum value of one average film stress is 0.1 to 20 MPa, and more preferably 0.1 to 10 MPa.
    [77] Average film stress σ (Pa) = Eh 2 / (1-ν) 6Rt
    [78] Where E / (1-ν) is the biaxial elastic modulus of the substrate, in the case of the silicon wafer, 1.805 × 10 −11 Pa, h is the thickness of the substrate (m), R is the radius of curvature of the substrate (m), and t is Thickness of the film (m).
    [79] By setting the maximum value of the average film stress at 0.1 to 20 MPa, shrinkage during firing can be suppressed, and plastic defects such as peeling and disconnection can be reduced, and plastic defects can be reduced by setting 0.1 to 10 MPa. The average film stress can be controlled by adding a urethane compound in the paste. When the paste contains a compound containing an ethylenically unsaturated group, the average film stress can be controlled by controlling the ethylenically unsaturated bond concentration.
    [80] The paste is usually a binder polymer, a dispersant, a plasticizer, a thickener, an organic solvent, an antisettling agent, an antioxidant, a reactive monomer. After combining various components such as a reactive oligomer, a reactive polymer, a photopolymerization initiator, a photoacid generator, a photobase generator, a sensitizer, a sensitizer, an ultraviolet absorber, an organic dye, an acid, a base, and an organic solvent to a predetermined composition, It is produced by mixing and dispersing homogeneously with three rollers or a mixer.
    [81] Although the viscosity of a paste is adjusted suitably according to addition ratio, such as an inorganic fine particle, a thickener, an organic solvent, a plasticizer, and a sedimentation inhibitor, the range is 2000-200,000 cps (centi poise) is preferable. For example, when applying to a substrate by the spin coat method, the viscosity of 200-500 cps is preferable. In order to apply | coat to a board | substrate by the screen printing method and to obtain a film thickness of 10-20 micrometers by one application | coating, the viscosity of 50,000-200,000 cps is preferable. When using the blade coater method, the die coater method, etc., the viscosity of 10,000-50,000 cps is preferable.
    [82] The display member can be obtained by apply | coating the paste of this invention obtained in this way on a board | substrate, forming a pattern using various methods, and baking. The paste of the present invention can be particularly suitably used for the manufacture of a plasma display member having partition walls on a substrate. As a method of forming a pattern, for example, a screen printing method, a sand blasting method, a photolithography method or the like can be used. The photolithography method is preferable because high precision processing is possible.
    [83] Although the example which manufactures a display member using the said paste by the photolithography technique is demonstrated, this invention is not limited to this.
    [84] The paste is applied to the entire surface or partially on the substrate to form a coating film. As a coating method, methods, such as a screen printing method, a bar coater, a roll coater, a die coater, and a blade coater, can be used. The coating thickness can be adjusted by selecting the number of coatings, the mesh of the screen and the viscosity of the paste.
    [85] When applying paste on a board | substrate here, in order to improve adhesiveness of a board | substrate and a coating film, surface treatment of a board | substrate can be performed. As surface treatment liquid, a silane coupling agent, for example, vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, tris (2-methoxyethoxy) vinylsilane, (gamma)-glycidoxy propyl trimethoxysilane , γ- (methacryloxypropyl) trimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ- Aminopropyl triethoxysilane, etc., or an organic metal, for example, organic titanium, organic aluminum, an organic zirconium, etc. can be used. Diluted silane coupling agent or organometal to an organic solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, etc. at a concentration of 0.1 to 5% use. Next, after apply | coating this surface treatment liquid uniformly on a board | substrate with a spinner etc., surface treatment can be performed by drying at 80-140 degreeC for 10 to 60 minutes.
    [86] After apply | coating, it exposes using an exposure apparatus. As an exposure apparatus, a proximity exposure machine etc. can be used. Moreover, when exposing large area, a large area can be exposed by the exposure machine of a small exposure area by exposing and conveying, after apply | coating paste on a board | substrate.
    [87] After exposure, image development is performed using the difference in solubility with respect to the developing solution of the exposed part and unexposed part of a coating film. The development is carried out by an immersion method, a spray method, or a blush method. As a developing solution, the organic solvent which can melt | dissolve the organic component in a paste can be used. In addition, water may be added to the organic solvent within a range not losing its solubility. It is preferable that a developing solution has water as a main component. When the compound which has acidic groups, such as a carboxyl group, exists in paste, it can develop with aqueous alkali solution. As the aqueous alkali solution, sodium hydroxide, sodium carbonate, calcium hydroxide aqueous solution and the like can be used, but an organic alkali aqueous solution is preferred because it is easy to remove the alkaline component during firing.
    [88] As the organic alkali, a general amine compound can be used. Specifically, tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine, etc. are mentioned.
    [89] The concentration of the aqueous alkali solution is usually 0.05 to 5% by weight, more preferably 0.1 to 1% by weight. If the alkali concentration is too low, the soluble portion is not removed. If the alkali concentration is too high, the pattern portion may be peeled off and the insoluble portion may be corroded. Moreover, it is preferable in process control that image development temperature at the time of image development is performed at 20-50 degreeC.
    [90] Next, firing is performed in a kiln. The firing atmosphere and temperature vary depending on the type of paste or substrate, but are fired in an atmosphere such as air, nitrogen, or hydrogen. As a kiln, a batch type kiln or a belt type continuous kiln can be used.
    [91] Firing is usually performed at 400 to 1000 ° C. When pattern-processing on a glass substrate, it is preferable to bake by hold | maintaining for 10 to 60 minutes at the temperature of 480-610 degreeC.
    [92] By the above process, the display member by which the pattern which consists of inorganic substance substantially was formed on the board | substrate is obtained.
    [93] Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited thereto. In addition, concentration (%) is weight% unless there is particular notice.
    [94] (Examples 1 to 10, Comparative Examples 1 and 2)
    [95] The urethane, the polymer solution, 3 weight% of dispersing agents, 3 weight% of leveling agents, and 4 weight% of dipropylene glycol monomethyl ethers shown in Table 1 were melt | dissolved heating at 50 degreeC, and the organic solution was prepared. The haze of the 30-micrometer-thick coating film obtained by apply | coating this on the glass substrate and drying for 90 minutes at 100 degreeC was measured using the direct reading haze computer HGM-2DP of Suga Test Machine Co., Ltd .. The measured values are shown in Table 2.
    [96] Inorganic fine particles of Table 1 were added to the organic solution and kneaded using a kneader to prepare a paste.
    [97] The weight when the said paste was made into 500 degreeC and 1000 degreeC by the temperature increase rate of 10 degree-C / min was measured in air using the thermogravimetric apparatus "TGA-50" by Shimadzu Corporation. Table 2 shows the values of (weight at 500 ° C) / (weight at 1000 ° C).
    [98] Subsequently, the paste was applied onto a silicon wafer having a diameter of 100 ± 0.5 mm and a thickness of 525 ± 25 μm manufactured by Shin-Etsu Chemical Co., Ltd., to form a coating film having a thickness of 3 to 10 μm. The stress at the time of heating up to 500 degreeC over 30 hours at 30 degreeC using the thin film stress measuring apparatus "F2300S" by FLEXUS company is measured. The maximum value of the measured stress is shown in Table 2.
    [99] Furthermore, the said paste was apply | coated on the glass substrate, the coating film of thickness 50micrometer was formed, and it baked at 15 minutes at 560 degreeC. After baking, the reflectance of the film which consists only of an inorganic substance was measured using the magnetic spectrophotometer "U-3210" by the Hitachi Seisakusho Corporation. The measured values are shown in Table 2.
    [100] A stripe-shaped silver electrode (line width 100 μm, thickness 3 μm, pitch 500 μm) was formed on a diagonal 42 inch glass substrate, and a dielectric layer having a thickness of 15 μm was formed thereon. Screen printing was done. A screen printing plate (horizontal partition: 500 μm line width, pattern pitch 1000 μm, vertical partition: line width 60 μm, pattern pitch 500 μm) for the purpose of forming a lattice-shaped partition wall pattern for plasma display. The printing and drying were repeated 5 to 6 times while setting the positions so as to be set in one batch so that the lower layer had a dry thickness of 90 µm.
    [101] Further, the above paste was used to screen-print the upper stripe pattern on the lower lattice partition pattern. A screen printing plate (vertical partition: 60 µm in line width and 500 µm in pattern pitch) was set in parallel with the address electrode, and printing and drying were repeated 5 to 6 times while aligning until the upper layer had a dry thickness of 90 µm.
    [102] The resulting grid-shaped partition wall pattern was further baked at 560 ° C. for 15 minutes, thereby forming a stripe-shaped partition wall having a pitch of 500 μm, a line width of 60 μm, and a height of 130 μm, and an orthogonal pitch of 1000 μm, a line width of 500 μm, and a height of 60 μm. A display member having a lattice-shaped partition wall composed of partition walls was obtained. Table 2 shows the results of observing defects such as peeling or disconnection after firing.
    [103] Next, a phosphor was applied between the partition walls adjacent to the display member. Application of the phosphor was performed by a dispenser method for ejecting the phosphor paste from the tip of the nozzle having a hole having a diameter of 130 µm. The phosphor was coated on the side surface of the partition so as to have a thickness of 25 µm after firing and a dielectric layer of 25 µm after firing, and then baked at 500 degrees for 10 minutes to prepare a back substrate for plasma display (hereinafter referred to as PDP). The separately prepared front substrate is sealed using the rear substrate and the sealing glass, and the neon gas containing 5% xenon is sealed to have an internal gas pressure of 66500 Pa. Furthermore, a drive circuit is mounted and a PDP is manufactured.
    [104] As the reliability evaluation of the created PDP, after leaving it to stand for 2 months without lighting, acceleration test is performed at 70 degreeC and 48 hours, and the voltage rise of an operating voltage is measured. The results are shown in Table 2. After the acceleration test, the case where the voltage rise was 1 V or less was stable, the case where 2 to 3 V was slightly increased, and the case where it was 4 V or more.
    [105] urethanePolymer solutionLow melting glassfillerOxide fine particlesKindsAddition amount (%)Weight average molecular weightEOKindsAddition amount (%)Addition amount (%)Addition amount (%)Addition amount (%) Example 1I101800030%I2060-- Example 2Ⅱ101900010%Ⅱ204020- Example 3Ⅲ10420000%I2060-- Example 4Ⅳ10270007%Ⅱ2040173 Example 5Ⅴ102400080%I2060-- Example 6Ⅵ10120050%Ⅱ2060-- Example 7I0.051800030%I2060-- Example 8Ⅱ251900010%Ⅱ205055 Example 9I101800030%I5030-- Example 10----I45405- Comparative Example 1----I3060-- Comparative Example 2----Ⅱ503010-
    [106] Haze (%) of organic coating filmWeight ratio (500 ℃ / 1000 ℃)Stress (MPa)reflectivity(%)Defects ()Operating voltage Example 10.21.016200stability Example 20.31.005430stability Example 370.01.004204stability Example 415.01.013610stability Example 50.11.0313204Little increase Example 60.01.0115205stability Example 70.11.0317205Little increase Example 80.11.004793stability Example 90.21.0411204Little increase Example 100.01.0416385Little increase Comparative Example 10.01.082420> 50increase Comparative Example 20.01.102548> 50increase
    [107] (Examples 11 to 21 and Comparative Examples 3 to 4)
    [108] The urethane, amine compound, monomer and polymer solutions shown in Table 3, 5% by weight of the photopolymerization initiator, 0.1% by weight of the organic dye O.O.5% by weight of γ-butyrolactone were dissolved while heating to 50 ° C to prepare an organic solution. The inorganic fine particles of Table 3 were added to the organic solution, and kneaded using a mixer to prepare a paste.
    [109] The haze of the organic component coating film, the weight of the paste at 500 ° C and 1000 ° C, the stress of the paste coating film, and the post-firing reflectance of the paste coating film were measured in the same manner as in Example 1. The measured values are shown in Table 4.
    [110] A stripe-shaped silver electrode (line width 50 μm, thickness 3 μm, pitch 250 μm) was formed on a diagonal 42 inch glass substrate, and a dielectric layer having a thickness of 15 μm was formed thereon, and then the paste was dried to a thickness of 90 μm. It applied and dried so that it might become micrometer.
    [111] Next, a photomask (stripe pattern, line width 600 µm, pattern pitch 1000 µm) for the purpose of forming a partition pattern for plasma display was set and exposed so as to be orthogonal to the address electrode. At this time, in order to prevent the said mask from being contaminated, 100 micrometers gaps were provided in the mask and the coating film surface. The smallest value was made into the lowest exposure amount among the exposure amounts in which peeling did not generate | occur | produce in the partition pattern at the time of image development.
    [112] After exposure, the paste was further applied and dried to form a coating film having a dry thickness of 90 탆. On this coating film, a photomask (stripe pattern, line width 30 micrometers, pattern pitch 250 micrometers) was set and exposed in parallel so that it may become parallel with an address electrode. After exposure, it developed in 0.5% of ethanolamine aqueous solution, and also baked at 560 degreeC for 15 minutes. A display member having a grid-shaped partition wall composed of a stripe-shaped partition wall having a pitch of 250 µm, a line width of 30 µm, and a height of 130 µm and an auxiliary partition wall having a pitch of 1000 µm, a line width of 600 µm and a height of 60 µm was obtained. After baking, defects, such as peeling and a disconnection, were observed. The results are shown in Table 4.
    [113] Next, a phosphor was applied between the partition walls adjacent to the display member. Application of the phosphor was performed by a dispenser method for ejecting the phosphor paste from the tip of the nozzle having a hole having a diameter of 130 µm. The phosphor was coated on the side surface of the partition to have a thickness of 25 μm and then fired on the dielectric layer to a thickness of 25 μm, and then baked at 500 ° C. for 10 minutes to prepare a PDP back substrate. The separately prepared front substrate is sealed using the rear substrate and the sealing glass, and the neon gas containing 5% xenon is sealed to have an internal gas pressure of 66500 Pa. In addition, a PDP is manufactured by mounting a driving circuit.
    [114] As the reliability evaluation of the created PDP, after leaving it to stand for 2 months without lighting, it accelerates test at 70 degreeC and 48 hours, and measures the voltage rise of an operating voltage. The results are shown in Table 4. The case where the voltage rise was 1 V or less was stable, the case of 2 to 3 V was slightly increased, and the case of 4 V or more was called an increase.
    [115] urethaneAmine compoundMonomerPolymer solutionLow melting glassfillerOxide fine particlesEthylenically unsaturated bond concentration (mol / kg)KindsAddition amount (%)Weight average molecular weightEOKindsAddition amount (%)KindsAddition amount (%)KindsAddition amount (%)AmountAddition amount (%)Addition amount (%) Example 11Ⅶ41800030%I3I3Ⅲ3050000.45 Example 12Ⅷ41900010%Ⅱ6-0Ⅳ30401000.83 Example 13Ⅶ41800030%-0I6Ⅲ3050000.36 Example 14Ⅷ0.051900010%Ⅱ5Ⅱ4.95Ⅲ3040730.83 Example 15Ⅶ251800030%-0-0Ⅳ1550000.25 Example 16Ⅲ4420000%I3Ⅱ3Ⅴ5030000.27 Example 17Ⅳ4270007%Ⅱ3I3Ⅲ4540500.66 Example 18Ⅴ42400080%I3I3Ⅳ4540500.61 Example 19Ⅵ4120050%Ⅱ3Ⅱ3Ⅴ3040550.39 Example 20-0--Ⅱ3Ⅱ7Ⅲ3050000.69 Example 21-0- I3I7Ⅳ30401000.61 Comparative Example 3-0--Ⅱ10-0Ⅲ3060001.19 Comparative Example 4-0--I0I5Ⅴ45301000.15
    [116] Haze (%) of organic coating filmWeight ratio (500 ℃ / 1000 ℃)Stress (MPa)reflectivity(%)Minimum exposure amount (mJ / ㎠)Defects ()Operating voltage Example 110.21.026205000stability Example 120.31.025433000stability Example 130.21.0242011000stability Example 140.31.0313613000Little increase Example 150.11.015205004stability Example 1672.01.003205004stability Example 1715.01.026384005stability Example 180.01.0414404005Little increase Example 190.01.0113795004stability Example 200.01.0517203007Little increase Example 210.01.0416454008Little increase Comparative Example 30.01.082420150> 50increase Comparative Example 40.01.1025531500> 50increase
    [117] (Examples 22 to 24, Comparative Example 5)
    [118] 2 weight% of a photoinitiator and 0.01 weight% of organic dye were melt | dissolved in the urethane, an amine compound, a monomer, and a polymer solution shown in Table 5, heating at 50 degreeC, and the organic solution was prepared. In addition, 70% by weight of silver fine particles (average particle size: 1.5 mu m, specific surface area: 1.1 m 2 / g) and 3% by weight of bismuth silicate glass fine particles were added and kneaded using a kneader to prepare a paste. Haze of the organic component coating film, the weight of the paste at 500 degreeC and 1000 degreeC, and the measurement of the stress of a paste coating film were made like Example 1. The measured values are shown in Table 6.
    [119] The silver fine particle paste obtained on the diagonal 42-inch glass substrate was apply | coated by screen printing, and the coating film of 6 micrometers of dry thicknesses was obtained. Then, it exposed through the photomask (stripe pattern, pattern pitch 250 micrometers, line width 100 micrometers). Furthermore, it developed in 0.5% ethanolamine aqueous solution and obtained the stripe-shaped electrode pattern. The glass substrate after electrode pattern processing was completed was dried at 80 degreeC for 15 minutes, and it baked at 580 degreeC for 15 minutes, and formed the electrode. Defects, such as peeling and a disconnection, were observed in the electrode pattern after baking. The results are shown in Table 6.
    [120] A dielectric layer was further formed on the glass substrate from which the electrode was manufactured, and a partition pattern was formed on the dielectric layer by the method of Example 11.
    [121] Next, a phosphor was applied between the partition walls adjacent to the display member. Application of the phosphor was performed by a dispenser method for discharging the phosphor paste from the tip of the nozzle having a hole having a diameter of 130 µm. The phosphor was coated on the side surface of the partition so as to have a thickness of 25 µm after firing and a dielectric layer of 25 µm after firing, and then baked at 500 degrees for 10 minutes to prepare a back substrate of the PDP. The separately prepared front substrate is sealed using the rear substrate and the sealing glass, and the neon gas containing 5% xenon is sealed to have an internal gas pressure of 66500 Pa. In addition, a PDP is manufactured by mounting a driving circuit.
    [122] urethaneAmine compoundMonomerPolymer solutionEthylenically unsaturated bond concentration (mol / kg)KindsAddition amount (%)Weight average molecular weightEOKindsAddition amount (%)KindsAddition amount (%)KindsAddition amount (%) Example 22Ⅶ41800030%I3Ⅲ3Ⅲ150.36 Example 23Ⅷ51900010%Ⅱ2-3Ⅳ150.41 Example 24Ⅶ71800030%-0Ⅲ3Ⅲ150.18 Comparative Example 5-0--Ⅱ9-OneⅣ151.05
    [123] Haze (%) of organic coating filmWeight ratio (500 ℃ / 1000 ℃)Stress (MPa)Minimum exposure amount (mJ / ㎠)Defects () Example 220.21.0264000 Example 230.31.0274500 Example 240.21.02411000 Comparative Example 50.31.1123300> 10
    [124] Polymer solution I: ethylcellulose (20 wt% terpineol solution),
    [125] Polymer solution II: polymethylmethacrylate (50% by weight toluene solution),
    [126] Polymer solution III: The polymer which added 40 weight part of glycidyl acrylates with respect to 100 weight part of copolymers to a styrene / methylmethacrylate / methacrylate copolymer (weight composition ratio 30/30/40),
    [127] Polymer solution IV: A polymer obtained by adding 40 parts by weight of glycidyl acrylate to 100 parts by weight of the copolymer to a methyl methacrylate / methacrylic acid copolymer (weight composition ratio 60/40) (resin acid value 115 mgKOH / g) ,
    [128] Polymer solution V: methyl methacrylate / methacrylate copolymer (weight composition ratio 82 / l8, resin acid value 90 mgKOH / g),
    [129] Monomer I: dipentaerythritol hexaacrylate,
    [130] Monomer II: CH 2 = C (CH 3 ) CO- (OCH (CH 3 ) CH 2 ) 9 -OCOC (CH 3 ) = CH 2 ,
    [131] Monomer III: propoxylated trimethylolpropane triacrylate,
    [132] Amine-I: N, N-diethylaminoethyl methacrylate,
    [133] Amine-II: bis (2-hydroxy-3-methacryloyloxypropyl) n-propylamine,
    [134] Urethane-I: In Chemical Formula 1, R 1 , R 2 are hydrogen, R 3 is an ethylene oxide-propylene oxide co-oligomer, R 4 is an isophorone diisocyanate residue, the content of ethylene oxide units is 30%, and the total molecular weight is 18,000. ,
    [135] Urethane-II: In Chemical Formula 1, R 1 , R 2 are hydrogen, R 3 is an ethylene oxide-propylene oxide copolymer, R 4 is an isophorone diisocyanate residue, and the content of ethylene oxide units is 10%, and the total molecular weight is 19,000. ,
    [136] Urethane-III: In Formula 1, R 1 , R 2 are hydrogen, R 3 is a butylene oxide oligomer, R 4 is an isophorone diisocyanate residue, the content of ethylene oxide units is 0%, the total molecular weight is 42,000,
    [137] Urethane-IV: In the general formula (1), R 1 and R 2 are hydrogen, R 3 is an ethylene oxide-butylene oxide co-oligomer, R 4 is an isophorone diisocyanate moiety, the content of ethylene oxide units is 7%, and the total molecular weight 27,000,
    [138] Urethane-V: In Chemical Formula 1, R 1 , R 2 are hydrogen, R 3 is an ethylene oxide-propylene oxide copolymer, R 4 is an isophorone diisocyanate residue, the content of ethylene oxide units is 80%, and the total molecular weight is 24,000,
    [139] Urethane-VI: In the general formula (1), R 1 , R 2 are hydrogen, R 8 is an ethylene oxide-propylene oxide copolymer, R 4 is a 1,4-cyclohexylene diisocyanate residue, and the content of ethylene oxide units is 50 %, The total molecular weight is 1,200,
    [140] Urethane-X: In Chemical Formula 1, R 1 and R 2 are methacryl groups, R 3 is an ethylene oxide-propylene oxide copolymer, R 4 is an isophorone diisocyanate residue, and the content of ethylene oxide units is 30%. The molecular weight is 18, O00,
    [141] Urethane-X: In Chemical Formula 1, R 1 and R 2 are acryl groups, R 3 is an ethylene oxide-propylene oxide co-oligomer, R 4 is a 1,4-cyclohexylene diisocyanate residue, and the content of ethylene oxide units is 10%, total molecular weight is l9,000,
    [142] Low melting glass powder: Li 2 O: 9%, SiO 2 : 22%, Al 2 O 3 23%, B 2 O 3 : 33%, BaO: 4%, ZnO: 2%, MgO: 7 % (Glass transition point 472 ° C., load softening point 515 ° C., refractive index 1.59, average particle diameter 2.55 μm),
    [143] Filler: In terms of oxide composition, SiO 2 : 38%, B 2 O 3 : 10%, BaO: 5%, Al 2 O 3 : 36%, ZnO: 2%, MgO: 5%, CaO 2 : 4% ( Glass transition point 652 ° C., load softening point 746 ° C., refractive index 1.59, average particle diameter 2.4 μm),
    [144] Oxide fine particles: oxide fine particles (average particle diameter: 0.005 mu m).
    [145] According to the paste of this invention, the display member without a defect in the pattern after baking can be provided.
    权利要求:
    Claims (52)
    [1" claim-type="Currently amended] Paste containing a urethane compound and inorganic fine particles.
    [2" claim-type="Currently amended] The paste according to claim 1, wherein the content of the inorganic fine particles in the paste is 40% by weight to 80% by weight.
    [3" claim-type="Currently amended] The paste according to claim 1, wherein the urethane compound has an ethylenically unsaturated group.
    [4" claim-type="Currently amended] The paste according to claim 1, wherein the urethane compound has a molecular weight of 15000 to 50000.
    [5" claim-type="Currently amended] The paste according to claim 1, wherein the content of the urethane compound in the paste is 0.1 wt% to 20 wt%.
    [6" claim-type="Currently amended] The paste of claim 1, wherein the urethane compound contains ethylene oxide units.
    [7" claim-type="Currently amended] The paste according to claim 1, wherein the urethane compound is represented by the following formula (1).
    <Formula 1>
    R 1- (R 4 -R 3 ) n -R 4 -R 2
    Here, R 1 and R 2 are selected from the group consisting of a substituent including an ethylenically unsaturated group, hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and a hydroxyaralkyl group, and may be the same or different. R 3 is an alkylene oxide group or an alkylene oxide oligomer, and R 4 is an organic group containing a urethane bond. n is a natural number of 1-10.
    [8" claim-type="Currently amended] The paste according to claim 7, wherein R 3 is an oligomer comprising an ethylene oxide unit and a propylene oxide unit, and the ethylene oxide unit content in the oligomer is in the range of 8 to 70% by weight.
    [9" claim-type="Currently amended] The paste according to claim 1, which further contains an amine compound having an ethylenically unsaturated group.
    [10" claim-type="Currently amended] The paste of Claim 9 whose amine compound is a compound represented by following formula (3) or (4).
    <Formula 3>
    R 5 R 6 R 7 N
    <Formula 4>
    R 5 R 6 NM-NR 7 R 8
    Here, R 5 is a substituent containing an ethylenically unsaturated group, R 6 , R 7 , R 8 is a substituent containing an ethylenically unsaturated group, hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group and a hydroxyalkyl group One selected from the group consisting of, R 6 , R 7 , R 8 may be the same or different. M represents a divalent linking group.
    [11" claim-type="Currently amended] The paste of Claim 1 which further contains the polymer which has a carboxyl group.
    [12" claim-type="Currently amended] The paste according to claim 11, wherein the polymer having a carboxyl group has an ethylenically unsaturated group.
    [13" claim-type="Currently amended] The paste according to claim 1, wherein the inorganic fine particles comprise a low melting glass powder having a load softening point of 450 to 600 ° C.
    [14" claim-type="Currently amended] The paste according to claim 1, wherein the inorganic fine particles contain 60 wt% to 97 wt% of the low melting glass powder and 3 wt% to 40 wt% of the filler having an average particle diameter of 1 µm to 4 µm.
    [15" claim-type="Currently amended] The paste according to claim 14, wherein the inorganic fine particles further contain 30% by weight or less of oxide fine particles having an average particle diameter of 0.003 to 0.02 µm.
    [16" claim-type="Currently amended] The paste of Claim 1 whose weight at the time of heating up to 500 degreeC and 1000 degreeC is represented by following Formula.
    (Weight at 500 ° C) / (weight at 1000 ° C) ≤1.05
    [17" claim-type="Currently amended] The paste of Claim 1 which apply | coated the paste of Claim 1 on a silicon wafer, and when it heated up to 500 degreeC, the paste whose average film stress calculated from the curvature of the silicon wafer by shrinkage of the said thin film is 0.1-20 MPa.
    [18" claim-type="Currently amended] The paste of claim 1 which is photosensitive.
    [19" claim-type="Currently amended] The paste according to claim 18, wherein the ethylenically unsaturated bond concentration in the paste is 0.2 to 1.0 mol per kg of paste before active light irradiation.
    [20" claim-type="Currently amended] The paste according to claim 1, which is used for display.
    [21" claim-type="Currently amended] The display paste of claim 20 wherein the display is a plasma display.
    [22" claim-type="Currently amended] A paste containing inorganic fine particles and an organic component, wherein the weight at the time of heating up to 500 degreeC and 100 degreeC is represented by following Formula.
    (Weight at 500 ° C) / (weight at 1000 ° C) ≤1.05
    [23" claim-type="Currently amended] As a paste containing an inorganic fine particle and an organic component, when the said paste is apply | coated on a silicon wafer, and a thin film was formed and it heated up to 500 degreeC, the maximum value of the average film stress computed from the curvature amount of the silicon wafer by shrinkage of a thin film is A paste that is from 0.1 to 20 MPa.
    [24" claim-type="Currently amended] A method of manufacturing a display member comprising the step of applying a paste containing a urethane compound and inorganic fine particles onto a substrate and baking the same.
    [25" claim-type="Currently amended] The method for producing a display member according to claim 24, wherein the content of the inorganic fine particles in the paste is 40% by weight to 80% by weight.
    [26" claim-type="Currently amended] The method for producing a display member according to claim 24, wherein the urethane compound has an ethylenically unsaturated group.
    [27" claim-type="Currently amended] The manufacturing method of the display member of Claim 24 whose molecular weight of a urethane compound is 15000-50000.
    [28" claim-type="Currently amended] The method for producing a display member according to claim 24, wherein the content of the urethane compound in the paste is 0.1 wt% to 20 wt%.
    [29" claim-type="Currently amended] The method for producing a display member according to claim 24, wherein the urethane compound contains ethylene oxide units.
    [30" claim-type="Currently amended] The manufacturing method of the display member of Claim 24 whose urethane compound is represented by following General formula (1).
    <Formula 1>
    R 1- (R 4 -R 3 ) n -R 4 -R 2
    Here, R 1 and R 2 may be the same or different from each other selected from the group consisting of a substituent including an ethylenically unsaturated group, hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and a hydroxyaralkyl group. R 3 is an alkylene oxide group or an alkylene oxide oligomer, and R 4 is an organic group containing a urethane bond. n is a natural number of 1-10.
    [31" claim-type="Currently amended] The method for producing a display member according to claim 30, wherein R 3 is an oligomer comprising an ethylene oxide unit and a propylene oxide unit, and the ethylene oxide unit content in the oligomer is in the range of 8 to 70% by weight.
    [32" claim-type="Currently amended] The method for producing a display member according to claim 24, wherein the paste also contains an amine compound having an ethylenically unsaturated group.
    [33" claim-type="Currently amended] 33. The method for producing a display member according to claim 32, wherein the amine compound is a compound represented by the following Chemical Formula 3 or 4.
    <Formula 3>
    R 5 R 6 R 7 N
    <Formula 4>
    R 5 R 6 NM-NR 7 R 8
    Here, R 5 is a substituent containing an ethylenically unsaturated group, R 6 , R 7 , R 8 is a substituent containing an ethylenically unsaturated group, hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group and a hydroxyalkyl group One selected from the group consisting of, R 6 , R 7 , R 8 may be the same or different. M represents a divalent linking group.
    [34" claim-type="Currently amended] The method for producing a display member according to claim 24, wherein the paste further contains a polymer having a carboxyl group.
    [35" claim-type="Currently amended] 35. The method for producing a display member according to claim 34, wherein the polymer having a carboxyl group has an ethylenically unsaturated group.
    [36" claim-type="Currently amended] The method for producing a display member according to claim 24, wherein the inorganic fine particles include low melting glass powder having a load softening point of 450 to 600 ° C.
    [37" claim-type="Currently amended] The method for producing a display member according to claim 24, wherein the inorganic fine particles contain 60 wt% to 97 wt% of the low melting point glass powder and 3 wt% to 40 wt% of the filler having an average particle diameter of 1 µm to 4 µm.
    [38" claim-type="Currently amended] 38. The method for producing a display member according to claim 37, wherein the inorganic fine particles further contain 30% by weight or less of oxide fine particles having an average particle diameter of 0.003 to 0.02 mu m.
    [39" claim-type="Currently amended] The manufacturing method of the display member which is a paste in which the weight when the paste of Claim 24 heated up to 500 degreeC and 1000 degreeC is represented by following Formula.
    (Weight at 500 ° C.) / (Weight at 1000 ° C.) ≦ l.05
    [40" claim-type="Currently amended] When the paste according to claim 24 is applied onto a silicon wafer to form a thin film and heated to 500 ° C., a paste having a maximum average film stress calculated from the warpage amount of the silicon wafer due to shrinkage of the thin film is 0.1 to 20 MPa. The manufacturing method of the display member to be used.
    [41" claim-type="Currently amended] 25. The method of claim 24, wherein the paste is photosensitive.
    [42" claim-type="Currently amended] The manufacturing method of the display member of Claim 41 which apply | coats a paste and pattern-processes by the photolithographic method, and then bakes.
    [43" claim-type="Currently amended] 42. The method of producing a display member according to claim 41, wherein the ethylenically unsaturated bond concentration in the paste is 0.2 to 1.0 mol per kg of paste before actinic light irradiation.
    [44" claim-type="Currently amended] 25. The method of claim 24, wherein the display is a plasma display.
    [45" claim-type="Currently amended] The display member manufactured by the method of Claim 24.
    [46" claim-type="Currently amended] A display made using the display member according to claim 45.
    [47" claim-type="Currently amended] The display of claim 46 which is a plasma display.
    [48" claim-type="Currently amended] The manufacturing method of the display member which includes the process of apply | coating and baking the paste of Claim 22 or 23 on a board | substrate.
    [49" claim-type="Currently amended] 49. The method of claim 48, wherein the display is a plasma display.
    [50" claim-type="Currently amended] A display member manufactured by the method of claim 48.
    [51" claim-type="Currently amended] A display made using the display member according to claim 50.
    [52" claim-type="Currently amended] The display of claim 51 which is a plasma display.
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    同族专利:
    公开号 | 公开日
    KR100832654B1|2008-05-27|
    CN1629726A|2005-06-22|
    EP1158019A2|2001-11-28|
    CN100392516C|2008-06-04|
    US20020008470A1|2002-01-24|
    US7411780B2|2008-08-12|
    US20050079447A1|2005-04-14|
    EP1158019B1|2007-12-26|
    MY130468A|2007-06-29|
    TW522435B|2003-03-01|
    CN1311295C|2007-04-18|
    US7004812B2|2006-02-28|
    JP4710169B2|2011-06-29|
    DE60132046T2|2008-12-11|
    EP1158019A3|2004-03-31|
    JP2002173597A|2002-06-21|
    CN1325038A|2001-12-05|
    DE60132046D1|2008-02-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-05-23|Priority to JP2000-151327
    2000-05-23|Priority to JP2000151327
    2000-06-19|Priority to JP2000182707
    2000-06-19|Priority to JP2000-182707
    2000-09-29|Priority to JP2000-298990
    2000-09-29|Priority to JP2000298990
    2001-05-22|Application filed by 히라이 가쯔히꼬, 도레이 가부시끼가이샤
    2001-12-07|Publication of KR20010107615A
    2008-05-27|Application granted
    2008-05-27|Publication of KR100832654B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP2000-151327|2000-05-23|
    JP2000151327|2000-05-23|
    JP2000182707|2000-06-19|
    JP2000-182707|2000-06-19|
    JP2000-298990|2000-09-29|
    JP2000298990|2000-09-29|
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