JP4452472B2 - Binder resin composition for glass paste and glass paste - Google Patents
Binder resin composition for glass paste and glass paste Download PDFInfo
- Publication number
- JP4452472B2 JP4452472B2 JP2003328162A JP2003328162A JP4452472B2 JP 4452472 B2 JP4452472 B2 JP 4452472B2 JP 2003328162 A JP2003328162 A JP 2003328162A JP 2003328162 A JP2003328162 A JP 2003328162A JP 4452472 B2 JP4452472 B2 JP 4452472B2
- Authority
- JP
- Japan
- Prior art keywords
- modified polyvinyl
- glass paste
- mol
- glass
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011521 glass Substances 0.000 title claims description 67
- 239000011342 resin composition Substances 0.000 title claims description 23
- 239000011230 binding agent Substances 0.000 title claims description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 31
- 239000011354 acetal resin Substances 0.000 claims description 31
- 229920006324 polyoxymethylene Polymers 0.000 claims description 31
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 31
- 229920002554 vinyl polymer Polymers 0.000 claims description 31
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 18
- 239000005977 Ethylene Substances 0.000 claims description 18
- 238000006359 acetalization reaction Methods 0.000 claims description 17
- 238000007127 saponification reaction Methods 0.000 claims description 16
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 15
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 8
- 150000001299 aldehydes Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000001856 Ethyl cellulose Substances 0.000 description 6
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 6
- 229920001249 ethyl cellulose Polymers 0.000 description 6
- 235000019325 ethyl cellulose Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- -1 thiol compounds Chemical class 0.000 description 4
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 3
- 229940088601 alpha-terpineol Drugs 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000075 oxide glass Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 2
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 description 1
- QENRKQYUEGJNNZ-UHFFFAOYSA-N 2-methyl-1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(C)C(S(O)(=O)=O)NC(=O)C=C QENRKQYUEGJNNZ-UHFFFAOYSA-N 0.000 description 1
- PVFYDPMTPBPRQA-UHFFFAOYSA-N 2-methylprop-2-enenitrile;prop-2-enenitrile Chemical compound C=CC#N.CC(=C)C#N PVFYDPMTPBPRQA-UHFFFAOYSA-N 0.000 description 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical class CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- TXDRMFQQROPOKK-UHFFFAOYSA-N [Si+2]=O.[B+]=O.[O-2].[Zn+2] Chemical compound [Si+2]=O.[B+]=O.[O-2].[Zn+2] TXDRMFQQROPOKK-UHFFFAOYSA-N 0.000 description 1
- 125000004036 acetal group Chemical group 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- DUYAAUVXQSMXQP-UHFFFAOYSA-N ethanethioic S-acid Chemical compound CC(S)=O DUYAAUVXQSMXQP-UHFFFAOYSA-N 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 1
- 229960003868 paraldehyde Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Glass Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Gas-Filled Discharge Tubes (AREA)
Description
本発明は、プラズマディスプレイパネルの製造工程で使用されるガラスペーストに利用されるバインダ樹脂組成物、及びそれを用いるガラスペーストに関する。 The present invention relates to a binder resin composition used for a glass paste used in a manufacturing process of a plasma display panel, and a glass paste using the same.
プラズマディスプレイパネルを製造する場合は、一般に次の様な工程で行われる。ガラス基板に表示電極、バス電極を形成する。さらに誘電体層、ＭｇＯ層を形成することで前面ガラス基板を作製する。一方、ガラス基板にデータ電極を形成し、誘電体層を形成し、 さらにバリアリブ、蛍光体層を形成することで背面ガラス基板を作製する。これらの前面ガラス基板、背面ガラス基板を張り合わせ、排気、放電ガスを封入した後、プリント基板を実装し、プラズマディスプレイパネルが完成する。 When manufacturing a plasma display panel, the following steps are generally performed. Display electrodes and bus electrodes are formed on a glass substrate. Furthermore, a front glass substrate is produced by forming a dielectric layer and an MgO layer. On the other hand, a data electrode is formed on a glass substrate, a dielectric layer is formed, and a barrier rib and a phosphor layer are further formed to produce a back glass substrate. These front glass substrate and rear glass substrate are bonded together, exhaust gas and discharge gas are sealed, and then a printed circuit board is mounted to complete a plasma display panel.
背面ガラス基板製造工程のうち、バリアリブは一般に次のようにして形成される。バリアリブ材を塗布し、ドライフィルムレジストをラミネートする。フォトマスクを通して露光、現像しパターンを形成する。その後、サンドブラストにてバリアリブ材をパターン状に切削し、残ったドライフィルムレジストを剥離した後、焼成する。バリアリブ材には一般に、ガラスペーストが使用されており、従来、ガラスペーストは、ガラス粉末、エチルセルロースやアクリル樹脂等のバインダ樹脂、α−テルピネオール、ブチルカルビトールアセテート等の溶剤から構成されている。バインダ樹脂には、一般にエチルセルロース樹脂やアクリル樹脂が使用されている。（特許文献１、特許文献２）
上記ガラスペースト用バインダ樹脂としてエチルセルロースを用いた場合、エチルセルロースの耐アルカリ性が低かったり、ガラスとの接着力が低いために、現像工程にて剥離が生じ、バリアリブが所望するパターンに形成されないという欠点があった。本発明は上記問題を解決し、その目的とするところは耐薬品性、特に耐アルカリ性に優れるガラスペースト用バインダ樹脂組成物を提供することを目的とする。 When ethyl cellulose is used as the binder resin for the glass paste, the alkali resistance of ethyl cellulose is low or the adhesive strength with glass is low, so that peeling occurs in the development process and the barrier ribs are not formed in the desired pattern. there were. The object of the present invention is to solve the above problems and to provide a binder resin composition for glass paste which is excellent in chemical resistance, particularly alkali resistance.
上記の目的を達成するためには、エチレン含有量１〜２０ｍｏｌ％、及びケン化度が８０ｍｏｌ％以上の変性ポリビニルアルコールをアセタール化した変性ポリビニルアセタール樹脂からなる樹脂組成物を用いる。特には、上記変性ポリビニルアセタール樹脂のアセタール化度が４０〜８０ｍｏｌ％であるもの、または上記エチレン含有量１〜２０ｍｏｌ％、及びケン化度が８０ｍｏｌ％以上の変性ポリビニルアルコールをブチルアルデヒド、及び／またはアセトアルデヒドでアセタール化した変性ポリビニルアセタール樹脂からなるガラスペースト用バインダ樹脂組成物が好ましい。 In order to achieve the above object, a resin composition comprising a modified polyvinyl acetal resin obtained by acetalizing a modified polyvinyl alcohol having an ethylene content of 1 to 20 mol% and a saponification degree of 80 mol% or more is used. In particular, the modified polyvinyl acetal resin having a degree of acetalization of 40 to 80 mol%, or a modified polyvinyl alcohol having an ethylene content of 1 to 20 mol% and a saponification degree of 80 mol% or more, butyraldehyde, and / or A binder resin composition for glass paste made of a modified polyvinyl acetal resin acetalized with acetaldehyde is preferred.
本発明のガラスペーストは、本発明のガラスペースト用バインダ樹脂組成物を用いるものである。 The glass paste of the present invention uses the binder resin composition for glass paste of the present invention.
以下、本発明を詳細に説明する。本発明のガラスペースト用バインダ樹脂組成物は、エチレン含有量１〜２０ｍｏｌ％、及びケン化度が８０ｍｏｌ％以上の変性ポリビニルアルコールをアセタール化したことを特徴とする変性ポリビニルアセタール樹脂からなる。 該変性ポリビニルアセタール樹脂は単独で、または、他の添加物と併用してガラスペースト用バインダ樹脂組成物とすることができる。 Hereinafter, the present invention will be described in detail. The binder resin composition for glass paste of the present invention comprises a modified polyvinyl acetal resin obtained by acetalizing a modified polyvinyl alcohol having an ethylene content of 1 to 20 mol% and a saponification degree of 80 mol% or more. The modified polyvinyl acetal resin can be used alone or in combination with other additives to form a binder resin composition for glass paste.
本発明に係る変性ポリビニルアルコールは、ビニルエステルとエチレンの共重合体をケン化することにより得られる。ビニルエステルとしては、蟻酸ビニル、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニルなどが挙げられるが、酢酸ビニルが経済的にみて好ましい。 The modified polyvinyl alcohol according to the present invention can be obtained by saponifying a copolymer of vinyl ester and ethylene. Examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate and the like, and vinyl acetate is preferable from the economical viewpoint.
エチレン単位の含有量は、１〜２０ｍｏｌ％であることが必要である。エチレンの含有量が１ｍｏｌ％未満の場合には、熱分解性の効果が顕著に発現せず、２０ｍｏｌ％を超える場合には上記変性ポリビニルアルコールの水溶性が低下するため変性ポリビニルアセタール樹脂のアセタール化反応が困難になったり、あるいは、できあがった変性ポリビニルアセタール樹脂の溶剤溶解性が悪くなり、ガラスペースト作製に支障が出たり、経時粘度安定性が悪くなることがある。 The ethylene unit content is required to be 1 to 20 mol%. When the ethylene content is less than 1 mol%, the effect of thermal decomposability is not remarkably exhibited, and when it exceeds 20 mol%, the water solubility of the modified polyvinyl alcohol decreases, so that the modified polyvinyl acetal resin is acetalized. The reaction may be difficult, or the resulting modified polyvinyl acetal resin may have poor solvent solubility, hindering the preparation of glass paste, and poor viscosity stability over time.
上記変性ポリビニルアルコールは、本発明の効果を損なわない範囲で、エチレン性不飽和単量体を共重合したものでも良い。このようなエチレン性不飽和単量体としては、例えば、アクリル酸、メタクリル酸、（無水）フタル酸、（無水）マレイン酸、（無水）イタコン酸、アクリロニトリルメタクリロニトリル、アクリルアミド、メタクリルアミド、トリメチル−（３−アクリルアミド−３−ジメチルプロピル）−アンモニウムクロリド、アクリルアミド−２−メチルプロパンスルホン酸、及びそのナトリウム塩、エチルビニルエーテル、ブチルビニルエーテル、Ｎ−ビニルピロリドン、塩化ビニル、臭化ビニル、フッ化ビニル、塩化ビニリデン、フッ化ビニリデン、テトラフルオロエチレン、ビニルスルホン酸ナトリウム、アリルスルホン酸ナトリウム等が挙げられる。また、チオール酢酸、メルカプトプロピオン酸等のチオール化合物の存在下で、酢酸ビニル等のビニルエステル系単量体とエチレンを共重合し、それをケン化することによって得られる末端変性ポリビニルアルコールも用いることができる。 The modified polyvinyl alcohol may be one obtained by copolymerizing an ethylenically unsaturated monomer as long as the effects of the present invention are not impaired. Examples of such ethylenically unsaturated monomers include acrylic acid, methacrylic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, acrylonitrile methacrylonitrile, acrylamide, methacrylamide, and trimethyl. -(3-acrylamido-3-dimethylpropyl) -ammonium chloride, acrylamido-2-methylpropanesulfonic acid and its sodium salt, ethyl vinyl ether, butyl vinyl ether, N-vinyl pyrrolidone, vinyl chloride, vinyl bromide, vinyl fluoride , Vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, sodium vinyl sulfonate, sodium allyl sulfonate and the like. Also use terminal-modified polyvinyl alcohol obtained by copolymerizing vinyl ester monomer such as vinyl acetate with ethylene in the presence of thiol compounds such as thiol acetic acid and mercaptopropionic acid, and saponifying it. Can do.
また、上記変性ポリビニルアルコールはエチレンのみによる変性が最も好ましい。該変性ポリビニルアルコールは水溶性である点、また、これを使用してアセタール化された変性ポリビニルアセタール樹脂溶液の経時粘度安定性の点などから、エチレン以外のコモノマーにより上記変性ポリビニルアルコールをさらに変性する場合には、該コモノマーの含有量は２．０ｍｏｌ％未満が好ましい。 The modified polyvinyl alcohol is most preferably modified with ethylene alone. The modified polyvinyl alcohol is further modified with a comonomer other than ethylene from the viewpoint that the modified polyvinyl alcohol is water-soluble, and the viscosity stability with time of the modified polyvinyl acetal resin solution acetalized using the modified polyvinyl alcohol. In some cases, the comonomer content is preferably less than 2.0 mol%.
また、上記変性ポリビニルアルコールのケン化度は、８０ｍｏｌ％以上であることが必要である。８０ｍｏｌ％未満では、変性ポリビニルアルコールの水への溶解性が悪くなるためアセタール化反応が困難になり、また、水酸基量が少ないとアセタール化反応自体が困難になるためである。 Further, the saponification degree of the modified polyvinyl alcohol needs to be 80 mol% or more. If the amount is less than 80 mol%, the solubility of the modified polyvinyl alcohol in water becomes poor, so that the acetalization reaction becomes difficult, and if the amount of hydroxyl groups is small, the acetalization reaction itself becomes difficult.
エチレン含有量が１〜２ｍｏｌ％の範囲であれば、上記変性ポリビニルアルコールを単独で使用してもよく、あるいは、変性ポリビニルアルコールと未変性ポリビニルアルコールを混合して使用し、最終的に得られた混合された変性ポリビニルアセタール樹脂の英金的なエチレン含有量が１〜２０ｍｏｌ％となるようにしても良い。 If the ethylene content is in the range of 1 to 2 mol%, the modified polyvinyl alcohol may be used alone, or the modified polyvinyl alcohol and unmodified polyvinyl alcohol are mixed and used, and finally obtained. The mixed modified polyvinyl acetal resin may have an English-gold ethylene content of 1 to 20 mol%.
また、ケン化度においては、アセタール化する際の変性ポリビニルアルコールのケン化度が８０ｍｏｌ％以上であれば、それを該変性ポリビニルアルコール単独、あるいは、ケン化度８０ｍｏｌ％以上の変性ポリビニルアルコールとケン化度８０ｍｏｌ％未満の変性ポリビニルアルコールを混合して、平均的なケン化度を８０ｍｏｌ％以上に調整してから使用しても良い。 In addition, regarding the saponification degree, if the saponification degree of the modified polyvinyl alcohol at the time of acetalization is 80 mol% or more, the modified polyvinyl alcohol alone or a modified polyvinyl alcohol having a saponification degree of 80 mol% or more and saponification can be used. A modified polyvinyl alcohol having a degree of conversion of less than 80 mol% may be mixed to adjust the average degree of saponification to 80 mol% or more before use.
本発明に係る変性ポリビニルアセタール樹脂は、上記変性ポリビニルアルコールをアセタール化することによって得られる。このような変性ポリビニルアセタール樹脂は、変性ポリビニルアルコールの水溶液に各種アルデヒドを添加し、公知の方法でアセタール化反応を行うことによって合成することができる。 The modified polyvinyl acetal resin according to the present invention is obtained by acetalizing the modified polyvinyl alcohol. Such a modified polyvinyl acetal resin can be synthesized by adding various aldehydes to an aqueous solution of modified polyvinyl alcohol and performing an acetalization reaction by a known method.
変性ポリビニルアルコールのアセタール化に用いるアルデヒドとしては、特に限定されるものではないが、例えばホルムアルデヒド（パラホルムアルデヒドを含む）、アセトアルデヒド（パラアセトアルデヒドを含む）、プロピオンアルデヒド、ブチルアルデヒド、アミルアルデヒド、ヘキシルアルデヒド、ヘプチルアルデヒド、２−エチルヘキシルアルデヒド、シクロヘキシルアルデヒド、フルフラール、グリオキザール、グルタルアルデヒド、ベンズアルデヒド、２−メチルベンズアルデヒド、３−メチルベンズアルデヒド、４−メチルベンズアルデヒド、ｐ−ヒドロキシベンズアルデヒド、ｍ−ヒドロキシベンズアルデヒド、フェニルアセトアルデヒド、β−フェニルプロピオンアルデヒド等が挙げられ、これらのアルデヒドが単独で或いは二種以上を組み合わせて用いられる。特に、アセトアルデヒド及び／またはブチルアルデヒドでアセタール化したものが好ましい。 The aldehyde used for acetalization of the modified polyvinyl alcohol is not particularly limited. For example, formaldehyde (including paraformaldehyde), acetaldehyde (including paraacetaldehyde), propionaldehyde, butyraldehyde, amylaldehyde, hexylaldehyde, Heptylaldehyde, 2-ethylhexylaldehyde, cyclohexylaldehyde, furfural, glyoxal, glutaraldehyde, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, β- Phenylpropionaldehyde and the like, and these aldehydes are There may be used in combination of two or more kinds. In particular, those acetalized with acetaldehyde and / or butyraldehyde are preferred.
上記変性ポリビニルアセタール樹脂のアセタール化度は、単独アルデヒド、混合アルデヒドのいずれを用いる場合でも、全アセタール化度で４０〜８０ｍｏｌ％の範囲が好ましい。全アセタール化度が４０ｍｏｌ％未満では樹脂が水溶性となり現像工程で溶解するしやすくなったり、有機溶剤に不溶となるためにガラスペースト作製に支障がでたりする。逆に、全アセタール化度が８０ｍｏｌ％を超えると、残存水酸基が少なくなって変性ポリビニルアセタール樹脂の強靱性が損なわれ、ガラスペーストを塗布した際の時の塗膜強度が低下することがある。 The degree of acetalization of the modified polyvinyl acetal resin is preferably in the range of 40 to 80 mol% in terms of the total acetalization degree regardless of whether a single aldehyde or a mixed aldehyde is used. If the total degree of acetalization is less than 40 mol%, the resin becomes water-soluble and becomes easy to dissolve in the development process, or becomes insoluble in an organic solvent, which hinders glass paste production. On the other hand, when the total degree of acetalization exceeds 80 mol%, the residual hydroxyl group is decreased, the toughness of the modified polyvinyl acetal resin is impaired, and the coating strength when the glass paste is applied may be lowered.
ここで記載したアセタール化度の計算方法としては、変性ポリビニルアセタール樹脂のアセタール基が２つの水酸基からアセタール化されて形成されていることから、アセタール化された２つの水酸基を数える方法で計算されたアセタール化度のｍｏｌ％とするものである。 As the calculation method of the degree of acetalization described here, since the acetal group of the modified polyvinyl acetal resin is formed by acetalization from two hydroxyl groups, it was calculated by a method of counting the two acetalized hydroxyl groups. This is the mol% of the degree of acetalization.
上記変性ポリビニルアセタール樹脂の重合度は特に限定はされないが、３００〜２４００の範囲であることが好ましい。重合度が３００未満ではガラスペースト塗布時の塗膜強度がなく、クラック等が入り易く、逆に重合度が２４００を超えるとガラスペースト粘度が高くなりすぎ、ハンドリング性を低下させる恐れがある。 The degree of polymerization of the modified polyvinyl acetal resin is not particularly limited, but is preferably in the range of 300 to 2400. If the degree of polymerization is less than 300, there is no coating strength at the time of applying the glass paste and cracks and the like easily occur. Conversely, if the degree of polymerization exceeds 2400, the viscosity of the glass paste becomes too high and the handling property may be lowered.
上記変性ポリビニルアセタール樹脂の製造方法の一例を、より具体的に説明する。まず、上記変性ポリビニルアルコールを水に溶解させる。次に、塩酸のような酸触媒の存在で、前記のアセタール化度を与えるように、所定量のアルデヒド、好ましくはアセトアルデヒド及び／またはブチルアルデヒドと反応させた後、水酸化ナトリウム等のアルカリで中和し、水洗、乾燥を行うことにより得られる。 An example of the method for producing the modified polyvinyl acetal resin will be described more specifically. First, the modified polyvinyl alcohol is dissolved in water. Next, in the presence of an acid catalyst such as hydrochloric acid, the mixture is reacted with a predetermined amount of aldehyde, preferably acetaldehyde and / or butyraldehyde so as to give the above-mentioned degree of acetalization, and then neutralized with an alkali such as sodium hydroxide. It can be obtained by mixing, washing with water and drying.
本発明のガラスペーストは、主にはガラス粉末と有機溶剤、及び本発明のガラスペースト用バインダ樹脂組成物で構成され、これらをブレンダーミル、３本ロール等の各種混合機を用いて混合することにより得られる。 The glass paste of the present invention is mainly composed of glass powder and an organic solvent, and the binder resin composition for glass paste of the present invention, and these are mixed using various blenders such as a blender mill and a three roll. Is obtained.
上記ガラス粉末としては、例えば、酸化鉛−酸化ホウ素−酸化ケイ素−酸化カルシウム系ガラス、酸化亜鉛−酸化ホウ素−酸化ケイ素系ガラス、酸化鉛−酸化亜鉛−酸化ホウ素−酸化ケイ素系ガラスなどが挙げられる。また、本発明の目的を損なわない範囲で、例えば、酸化アルミニウム等を添加しても良い。 Examples of the glass powder include lead oxide-boron oxide-silicon oxide-calcium oxide glass, zinc oxide-boron oxide-silicon oxide glass, lead oxide-zinc oxide-boron oxide-silicon oxide glass, and the like. . Moreover, you may add aluminum oxide etc., for example in the range which does not impair the objective of this invention.
ガラス粉末の平均粒径は、０．０５〜１０μｍが好ましく、小さいと焼成時にバリアリブが倒壊しやすくなり、大きいと緻密なバリアリブが作製することが困難となる。 The average particle diameter of the glass powder is preferably 0.05 to 10 μm. If the glass powder is small, the barrier ribs are likely to collapse during firing, and if it is large, it is difficult to produce a dense barrier rib.
また、上記有機溶剤としては、本発明のガラスペースト用バインダ樹脂組成物を溶解しうるものであれば良く、特に限定されるものではない。一般にはα−テルピネオール、ブチルカルビトールアセテート、トルエン、キシレン等の芳香族炭化水素、メタノール、エタノール、イソプロパノール等のアルコール類、ジエチルケトン、ジブチルケトン、ジプロピルケトン、メチルエチルケトン等のケトン類、プロピオン酸メチル、プロピオン酸エチル、ヘキサン酸エチル等のエステル類やこれらの混合溶剤が用いられる。 The organic solvent is not particularly limited as long as it can dissolve the binder resin composition for glass paste of the present invention. In general, α-terpineol, butyl carbitol acetate, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol and isopropanol, ketones such as diethyl ketone, dibutyl ketone, dipropyl ketone and methyl ethyl ketone, methyl propionate Esters such as ethyl propionate and ethyl hexanoate and mixed solvents thereof are used.
尚、本発明のガラスペーストには、本発明の効果を損なわない程度に、適宜、可塑剤、潤滑剤、分散剤、帯電防止剤等を添加してもよい。 In addition, you may add a plasticizer, a lubricant, a dispersing agent, an antistatic agent, etc. to the glass paste of this invention suitably in such an extent that the effect of this invention is not impaired.
本発明のガラスペースト用バインダ樹脂組成物としては、エチレン含有量１〜２０ｍｏｌ％、及びケン化度が８０ｍｏｌ％以上の変性ポリビニルアルコールをアセタール化した変性ポリビニルアセタール樹脂単体を使用するか、もしくは本発明の効果を損なわない程度に該変性ポリビニルアセタール樹脂と他のバインダ樹脂、例えば、アクリル系樹脂、セルロース系樹脂、ポリビニルアセタール樹脂等を適宜組合せて使用してもかまわない。このような場合、例えばエチルセルロースのような対アルカリ性の低い樹脂との組合せでは、該変性ポリビニルアセタール樹脂の混合量としては３０重量％以上が望ましい。 As the binder resin composition for a glass paste of the present invention, a modified polyvinyl acetal resin obtained by acetalizing a modified polyvinyl alcohol having an ethylene content of 1 to 20 mol% and a saponification degree of 80 mol% or more is used. The modified polyvinyl acetal resin and another binder resin, for example, an acrylic resin, a cellulose resin, a polyvinyl acetal resin, or the like may be used in an appropriate combination to such an extent that the above effect is not impaired. In such a case, for example, in a combination with a resin having low alkalinity such as ethyl cellulose, the mixing amount of the modified polyvinyl acetal resin is preferably 30% by weight or more.
また、本発明のガラスペースト用バインダ樹脂組成物を用いてガラスペーストを作成する場合の含有量としては、使用するガラス粉末１００重量部に対して、２〜４０重量部が好ましく、さらには４〜２５重量部が好ましい。４重量部未満では、ガラス粉末を確実に結着することができず、逆に２５重量部より多くなるとガラスペースト用バインダ樹脂組成物の焼成に長時間を要したり、焼結後に残さが残りやすくなったりする。 Moreover, as content when creating a glass paste using the binder resin composition for glass pastes of this invention, 2-40 weight part is preferable with respect to 100 weight part of glass powder to be used, Furthermore, 4- 25 parts by weight is preferred. If the amount is less than 4 parts by weight, the glass powder cannot be reliably bound. Conversely, if the amount exceeds 25 parts by weight, it takes a long time to fire the binder resin composition for glass paste, or a residue remains after sintering. It becomes easy.
上述したように、本発明の変性ポリビニルアセタール樹脂からなるガラスペースト用バイン樹脂組成物を用いることより、現像工程での耐アルカリ性及びガラス基板との接着性に優れるガラスペーストを作製することができる。 As described above, by using the vine resin composition for glass paste made of the modified polyvinyl acetal resin of the present invention, a glass paste having excellent alkali resistance and adhesion to a glass substrate in the development process can be produced.
（実施例１）
（変性ポリビニルアセタール樹脂の合成）
重合度１７００、エチレン含有量１０ｍｏｌ％、ケン化度８８ｍｏｌ％の変性ポリビニルアルコール１９３ｇを純水２９００ｇに加え、９０℃の温度で約２時間攪拌し溶解させた。この溶液を２８℃に冷却し、これに濃度３５重量％の塩酸２０ｇとｎ−ブチルアルデヒド１１５ｇとを添加し、液温を２０℃に下げてこの温度を保持してアセタール化反応を行い、反応生成物を析出させた。その後、液温を３０℃、５時間保持して反応を完了させ、常法により中和、水洗及び乾燥を経て、変性ポリビニルアセタール樹脂の白色粉末を得た。
Example 1
(Synthesis of modified polyvinyl acetal resin)
193 g of modified polyvinyl alcohol having a polymerization degree of 1700, an ethylene content of 10 mol% and a saponification degree of 88 mol% was added to 2900 g of pure water, and the mixture was stirred and dissolved at a temperature of 90 ° C. for about 2 hours. This solution is cooled to 28 ° C., 20 g of hydrochloric acid having a concentration of 35% by weight and 115 g of n-butyraldehyde are added thereto, the liquid temperature is lowered to 20 ° C., and this temperature is maintained to carry out an acetalization reaction. The product precipitated out. Thereafter, the liquid temperature was kept at 30 ° C. for 5 hours to complete the reaction, and neutralized, washed with water and dried by a conventional method to obtain a white powder of a modified polyvinyl acetal resin.
得られたポリビニルアセタール樹脂を ＤＭＳＯ−ｄ６（重水素化ジメチルスルホキサイド）に溶解し、１３Ｃ−ＮＭＲ（核磁気共鳴スペクトル）を用いてアセタール化度を測定したところ、ブチラール化度は６５ｍｏｌ％であった。 The obtained polyvinyl acetal resin was dissolved in DMSO-d6 (deuterated dimethyl sulfoxide), and the degree of acetalization was measured using 13C-NMR (nuclear magnetic resonance spectrum). The degree of butyralization was 65 mol%. there were.
（ガラスペーストの作製）
続いて、酸化鉛−酸化ホウ素−酸化ケイ素−酸化アルミニウム系ガラス粉末（それぞれの組成：６６重量％、５重量％、２４重量％、５重量％）１００重量部とガラスペースト用バインダ樹脂組成物として上記変性ポリビニルアセタール樹脂５重量部、及び溶剤としてα−テルピネオール３０重量部をボールミルで混合することでガラスペーストを調製した。
(Production of glass paste)
Subsequently, 100 parts by weight of lead oxide-boron oxide-silicon oxide-aluminum oxide glass powder (respective compositions: 66 wt%, 5 wt%, 24 wt%, 5 wt%) and a binder resin composition for glass paste A glass paste was prepared by mixing 5 parts by weight of the modified polyvinyl acetal resin and 30 parts by weight of α-terpineol as a solvent with a ball mill.
（実施例２）
重合度１０００、エチレン含有量１０ｍｏｌ％、ケン化度８８ｍｏｌ％の変性ポリビニルアルコールを用いた以外は実施例１と同様の操作を行い変性ポリビニルアセタール樹脂を作成し、ガラスペースト用樹脂組成物として、実施例１と同様にしてガラスペーストを作製した。
(Example 2)
A modified polyvinyl acetal resin was prepared in the same manner as in Example 1 except that a modified polyvinyl alcohol having a polymerization degree of 1000, an ethylene content of 10 mol%, and a saponification degree of 88 mol% was used. A glass paste was prepared in the same manner as in Example 1.
（実施例３）
重合度８００、エチレン含有量１０ｍｏｌ％、ケン化度８８ｍｏｌ％の変性ポリビニルアルコールを用いて実施例１と同様の操作を行い変性ポリビニルアセタール樹脂を作成しポリビニルブチラール樹脂（積水化学工業製、エスレックＢ「ＢＭ−Ｓ」）との重量比６：４の混合樹脂を作成しガラスペースト用樹脂組成物を作製し、これを用いてガラスペーストを作製した。
(Example 3)
A modified polyvinyl acetal resin was prepared by performing the same operation as in Example 1 using a modified polyvinyl alcohol having a polymerization degree of 800, an ethylene content of 10 mol%, and a saponification degree of 88 mol%, and a polyvinyl butyral resin (Surek Chemical Co., Ltd., ESREC B " A mixed resin having a weight ratio of 6: 4 to BM-S ") was prepared to prepare a resin composition for glass paste, and this was used to prepare a glass paste.
（実施例４）
重合度６００、エチレン含有量 ５ｍｏｌ％、ケン化度９３ｍｏｌ％の変性ポリビニルアルコール、及びアセタール化させるアルデヒドとしてｎ−ブチルアルデヒドとアセトアルデヒドの重量比で２：１の混合物を用いた以外は実施例１と同様の操作を行いガラスペースト用樹脂組成物を作製し、これを用いてガラスペーストを作製した。
Example 4
Example 1 except that a modified polyvinyl alcohol having a polymerization degree of 600, an ethylene content of 5 mol%, a saponification degree of 93 mol%, and a mixture of n-butyraldehyde and acetaldehyde in a weight ratio of 2: 1 were used as the aldehyde to be acetalized. The same operation was performed to prepare a resin composition for glass paste, and a glass paste was prepared using this.
（比較例１）
ガラスペースト用バインダ樹脂組成物として、エチルセルロース（ダウケミカル製「ＳＴＤ型」）を用いた以外は実施例１と同様の操作を行ないガラスペーストを作成した。
(Comparative Example 1)
A glass paste was prepared in the same manner as in Example 1 except that ethyl cellulose (“STD type” manufactured by Dow Chemical) was used as the binder resin composition for glass paste.
実施例１〜４、比較例１で得られたガラスペーストをガラス基板状に塗布し、１００℃で６０分乾燥した。乾燥後、感光性レジストフィルムをラミネートし、ついで１ｍｍピッチのパターンを介して２５０ｍＪ／ｃｍ2で露光した。ついで、０．５％炭酸水素ナトリウム水溶液に浸漬し、塗布膜の状態を観察した。その結果、実施例１〜４の変性ポリビニルアセタール樹脂を用いた場合においては、１００秒浸漬してもレジストフィルムの剥離が認められず、また、３００秒浸漬後もガラス塗膜に変化が認められなかったのに対して、比較例１のものでは３０秒の浸漬でレジスト膜が剥離し、また、３００秒浸漬後はガラス膜の一部が剥離していることが認められた。 The glass pastes obtained in Examples 1 to 4 and Comparative Example 1 were coated on a glass substrate and dried at 100 ° C. for 60 minutes. After drying, a photosensitive resist film was laminated, and then exposed at 250 mJ / cm 2 through a 1 mm pitch pattern. Subsequently, it was immersed in a 0.5% aqueous sodium hydrogen carbonate solution, and the state of the coating film was observed. As a result, in the case where the modified polyvinyl acetal resins of Examples 1 to 4 were used, the resist film was not peeled off even after 100 seconds of immersion, and changes were observed in the glass coating after 300 seconds of immersion. In contrast, in the case of Comparative Example 1, it was confirmed that the resist film was peeled off after 30 seconds of immersion, and part of the glass film was peeled off after 300 seconds of immersion.
本発明のガラスペースト用バイン樹脂組成物は、ガラスペーストに用いられ、プラズマディスプレイパネルの製造工程で使用される。
The vine resin composition for glass paste of the present invention is used for glass paste and used in the manufacturing process of a plasma display panel.
Claims (4)
The glass paste containing the binder resin composition for glass pastes and glass powder of any one of Claims 1-3.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003328162A JP4452472B2 (en) | 2003-09-19 | 2003-09-19 | Binder resin composition for glass paste and glass paste |
| PCT/JP2004/009127 WO2005007710A1 (en) | 2003-06-26 | 2004-06-28 | Binder resin for coating paste |
| CN2004800174154A CN1809598B (en) | 2003-06-26 | 2004-06-28 | Binder resin for coating paste |
| KR1020057024665A KR101109809B1 (en) | 2003-06-26 | 2004-06-28 | Binder resin for coating paste |
| EP04746596A EP1637546B1 (en) | 2003-06-26 | 2004-06-28 | Binder resin for coating paste |
| DE602004024991T DE602004024991D1 (en) | 2003-06-26 | 2004-06-28 | BINDER FOR COATING PASTE |
| US10/561,971 US7569166B2 (en) | 2003-06-26 | 2004-06-28 | Binder resin for coating paste |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003328162A JP4452472B2 (en) | 2003-09-19 | 2003-09-19 | Binder resin composition for glass paste and glass paste |
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| JP2005089695A JP2005089695A (en) | 2005-04-07 |
| JP4452472B2 true JP4452472B2 (en) | 2010-04-21 |
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| JP2006299030A (en) * | 2005-04-19 | 2006-11-02 | Sekisui Chem Co Ltd | Vehicle for coating paste, and coating paste |
| JP5074761B2 (en) * | 2006-11-06 | 2012-11-14 | 積水化学工業株式会社 | Glass paste and plasma display panel manufacturing method |
| JP5291299B2 (en) * | 2007-05-17 | 2013-09-18 | 積水化学工業株式会社 | Conductive paste |
| WO2021060540A1 (en) * | 2019-09-26 | 2021-04-01 | 住友金属鉱山株式会社 | Electroconductive composition, electroconductive paste, electronic component, and laminated ceramic capacitor |
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