JP2014198767A - Modified polyvinyl acetal resin - Google Patents
Modified polyvinyl acetal resin Download PDFInfo
- Publication number
- JP2014198767A JP2014198767A JP2013074351A JP2013074351A JP2014198767A JP 2014198767 A JP2014198767 A JP 2014198767A JP 2013074351 A JP2013074351 A JP 2013074351A JP 2013074351 A JP2013074351 A JP 2013074351A JP 2014198767 A JP2014198767 A JP 2014198767A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl acetal
- modified polyvinyl
- acetal resin
- mol
- sulfonic acid
- 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.)
- Granted
Links
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 67
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000011354 acetal resin Substances 0.000 title claims abstract description 63
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 63
- 239000000919 ceramic Substances 0.000 claims abstract description 44
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 31
- 239000004711 α-olefin Substances 0.000 claims abstract description 19
- 150000001241 acetals Chemical group 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 238000007639 printing Methods 0.000 abstract description 14
- 230000009974 thixotropic effect Effects 0.000 abstract description 3
- 230000000740 bleeding effect Effects 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 27
- 239000011347 resin Substances 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 150000001299 aldehydes Chemical class 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000003960 organic solvent Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 238000006359 acetalization reaction Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 11
- -1 polyethylene terephthalate Polymers 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 238000007127 saponification reaction Methods 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 3
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 3
- 239000003985 ceramic capacitor Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 3
- UUKHCUPMVISNFW-UHFFFAOYSA-L disodium;4-formylbenzene-1,3-disulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC=C(C=O)C(S([O-])(=O)=O)=C1 UUKHCUPMVISNFW-UHFFFAOYSA-L 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229940116411 terpineol Drugs 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-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
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- 241001024304 Mino Species 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 2
- HNBDRPTVWVGKBR-UHFFFAOYSA-N methyl pentanoate Chemical compound CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HBNHCGDYYBMKJN-UHFFFAOYSA-N 2-(4-methylcyclohexyl)propan-2-yl acetate Chemical compound CC1CCC(C(C)(C)OC(C)=O)CC1 HBNHCGDYYBMKJN-UHFFFAOYSA-N 0.000 description 1
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 1
- LFEQNZNCKDNGRM-UHFFFAOYSA-N 2-ethylhexyl butanoate Chemical compound CCCCC(CC)COC(=O)CCC LFEQNZNCKDNGRM-UHFFFAOYSA-N 0.000 description 1
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 1
- BKZMFCVWBWMBEM-UHFFFAOYSA-N 3-methylbenzaldehyde;4-methylbenzaldehyde Chemical compound CC1=CC=C(C=O)C=C1.CC1=CC=CC(C=O)=C1 BKZMFCVWBWMBEM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKJADYKTJJGKDX-UHFFFAOYSA-N Butyl pentanoate Chemical compound CCCCOC(=O)CCCC OKJADYKTJJGKDX-UHFFFAOYSA-N 0.000 description 1
- RPRPDTXKGSIXMD-UHFFFAOYSA-N Caproic acid n-butyl ester Natural products CCCCCC(=O)OCCCC RPRPDTXKGSIXMD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002515 CoAl Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241001137307 Cyprinodon variegatus Species 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 1
- ICMAFTSLXCXHRK-UHFFFAOYSA-N Ethyl pentanoate Chemical compound CCCCC(=O)OCC ICMAFTSLXCXHRK-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 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
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002635 aromatic organic solvent Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- URCJRDMSDWTSGZ-UHFFFAOYSA-N benzaldehyde;sodium Chemical compound [Na].O=CC1=CC=CC=C1 URCJRDMSDWTSGZ-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 150000001656 butanoic acid esters Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical group C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 1
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 239000012188 paraffin wax Substances 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- IAHIMVFWYADCJJ-UHFFFAOYSA-N prop-1-enylcyclohexane Chemical group CC=CC1CCCCC1 IAHIMVFWYADCJJ-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- FZPPRCKGVCCJSG-UHFFFAOYSA-M sodium;4-formylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=O)C=C1 FZPPRCKGVCCJSG-UHFFFAOYSA-M 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/6342—Polyvinylacetals, e.g. polyvinylbutyral [PVB]
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
- C04B2235/3234—Titanates, not containing zirconia
- C04B2235/3236—Alkaline earth titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
- C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Ceramic Capacitors (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、低粘度でハイソリッド化が可能であり、かつ、チキソトロピー性に優れ、印刷時の糸引き、目詰まり及びニジミを抑制することが可能な変性ポリビニルアセタール樹脂、並びに、該変性ポリビニルアセタール樹脂を用いてなるセラミックグリーンシート用スラリー組成物及びセラミックグリーンシートに関する。 The present invention relates to a modified polyvinyl acetal resin that can be made into a high solid with a low viscosity, has excellent thixotropy, and can suppress stringing, clogging, and blurring during printing, and the modified polyvinyl acetal The present invention relates to a slurry composition for ceramic green sheets using a resin and a ceramic green sheet.
ポリビニルブチラール樹脂等のポリビニルアセタール樹脂は、強靱性、造膜性、顔料等の無機・有機粉体等の分散性、塗布面への接着性等に優れていることから、例えば、インク、塗料、焼付け用エナメル、ウォッシュプライマー、ラッカー、分散剤、接着剤、セラミックスグリーンシート、熱現像性感光材料、水性インク受容層等のバインダー等の様々な用途で使用されている。 Polyvinyl acetal resins such as polyvinyl butyral resins are excellent in toughness, film-forming properties, dispersibility of inorganic and organic powders such as pigments, adhesion to coated surfaces, etc. It is used in various applications such as printing enamels, wash primers, lacquers, dispersants, adhesives, ceramic green sheets, heat-developable photosensitive materials, and binders for aqueous ink receiving layers.
この中でもセラミックグリーンシートは、以下のような手法によって製造されている。すなわち、ポリビニルブチラール樹脂などのバインダー樹脂を有機溶剤に溶解した溶液に可塑剤、分散剤などを添加した後、セラミック原料粉末を加え、ボールミルにより均一に混合し、脱泡後に一定粘度を有するセラミックスラリー組成物を得る。このスラリー組成物をドクターブレード、リバースロールコーターなどを用いて、離型処理したポリエチレンテレフタレートフィルム又はＳＵＳプレートなどの支持体面に流延成形する。これを加熱することにより、有機溶剤の揮発分を溜去させた後、支持体から剥離することによって得られる。 Among these, the ceramic green sheet is manufactured by the following method. That is, after adding a plasticizer, a dispersing agent, etc. to a solution in which a binder resin such as polyvinyl butyral resin is dissolved in an organic solvent, a ceramic raw material powder is added, mixed uniformly by a ball mill, and a ceramic slurry having a constant viscosity after defoaming A composition is obtained. This slurry composition is cast on a support surface such as a polyethylene terephthalate film or a SUS plate which has been subjected to a release treatment using a doctor blade, a reverse roll coater or the like. By heating this, the volatile matter of the organic solvent is distilled off, and then it is obtained by peeling from the support.
近年、積層セラミックコンデンサを小型化、高容量化する目的で、セラミックグリーンシートの薄層化や多層化が進められている。しかしながら、セラミックグリーンシートの薄層化や多層化が進むにつれ、導電ペーストが印刷されている部分とされていない部分との段差が大きくなり、積層体を加熱圧着する際に、層間剥離（デラミネーション）やセラミックグリーンシート及び内部電極層の変形が生じて、積層セラミックコンデンサの電気特性や信頼性が低下するという問題が生じた。 In recent years, ceramic green sheets have been made thinner and multilayered for the purpose of reducing the size and increasing the capacity of multilayer ceramic capacitors. However, as the ceramic green sheets become thinner and multi-layered, the level difference between the part where the conductive paste is printed and the part where the conductive paste is not printed increases, and delamination (delamination) occurs when the laminate is heat-pressed. ) Or the deformation of the ceramic green sheet and the internal electrode layer, resulting in a problem that the electrical characteristics and reliability of the multilayer ceramic capacitor deteriorate.
このような欠点を解消するポリビニルアセタール樹脂として、特許文献１に示すような変性ポリビニルアセタール樹脂を含有する導電ペースト用バインダー樹脂が提案されている。このような変性ポリビニルアセタール樹脂では、デラミネーションを抑制することは可能であるが、スクリーン印刷時の糸引き、目詰まり及びニジミといった問題を完全に解消することはできず、積層セラミックコンデンサの更なる小型化、高容量化に対応するために、塗工ペーストに近年求められている印刷性能を完全に満足しているとはいえなかった。
なお、糸引きとは、スクリーン印刷に用いるスクリーン版から塗工ペーストがきれいに離れず、印刷面が糸を引いた状態になることをいい、目詰まりとは、スクリーン版の目に塗工ペーストが詰まって印刷できなくなる現象をいう。糸引きや目詰まりは、剪断速度が速い状態において塗工ペーストの見かけ粘度が高い場合に発生する。一方、ニジミとは、印刷した塗工ペーストがセラミックグリーンシート上で流動し、目的の印刷形状よりも拡がった状態で印刷されてしまう現象をいい、これは、剪断速度が遅い状態及び剪断されていない状態において塗工ペーストの見かけ粘度が低い場合に発生する。
As a polyvinyl acetal resin that eliminates such drawbacks, a binder resin for conductive paste containing a modified polyvinyl acetal resin as shown in Patent Document 1 has been proposed. With such a modified polyvinyl acetal resin, it is possible to suppress delamination, but problems such as stringing, clogging, and blurring at the time of screen printing cannot be completely eliminated. In order to cope with the reduction in size and increase in capacity, it has not been said that the printing performance required for coating paste in recent years is completely satisfied.
Thread drawing means that the coating paste does not leave cleanly from the screen plate used for screen printing, and the printed surface is in a state where the thread is pulled. Clogging is clogging means that the coating paste is in the eyes of the screen plate. A phenomenon that prevents printing due to clogging. Stringing or clogging occurs when the apparent viscosity of the coating paste is high at a high shear rate. On the other hand, the term “brightening” refers to a phenomenon in which a printed coating paste flows on a ceramic green sheet and is printed in a state where it is wider than the intended printing shape. Occurs when the apparent viscosity of the coating paste is low.
そのため、剪断速度が速い状態においては見かけ粘度が低くなり、かつ、剪断速度が遅い状態及び剪断されていない状態においては見かけ粘度が高くなる塗工ペースト、即ち、チキソトロピー性に優れた塗工ペーストを得ることができるポリビニルアセタール樹脂が求められていた。 Therefore, a coating paste having a low apparent viscosity when the shear rate is high and a high apparent viscosity when the shear rate is low and not sheared, that is, a coating paste excellent in thixotropic properties. There is a need for a polyvinyl acetal resin that can be obtained.
チキソトロピー性の改善に関しては、これまでにポリビニルアセタール樹脂にカルボキシル基、スルホン酸基などの極性置換基を導入する方法が知られている。特許文献２には、スルホン酸変性基を導入した変性ポリビニルアセタールに関する提案がなされているが、インク塗料用に低粘度化を示すことに関する提案であった。 Regarding the improvement of thixotropy, a method of introducing a polar substituent such as a carboxyl group or a sulfonic acid group into a polyvinyl acetal resin has been known so far. Patent Document 2 proposes a modified polyvinyl acetal in which a sulfonic acid-modified group is introduced, but it is a proposal related to showing a low viscosity for an ink paint.
また、環境保護の観点においては、芳香族系溶剤のトルエン、キシレン等を使用せずに、エタノール、プロパノール等のアルコール系の単独溶剤への溶解性に優れたポリビニルアセタール樹脂を使用する頻度が増している。環境保護の観点においては、自動車におけるＶＯＣ規制に見られるように、ハイソリッド化、水性化、粉体化の大きな三つの流れがある。特にハイソリッド化は他の２つに比べて設備投資が要らず、使用溶剤を少なくし、固形分濃度を高くするだけであり、性能を従来品から推測でき保証できるため、盛んに取り組みが行われている。ポリビニルアセタール樹脂を用いてハイソリッド化を実現する方法としては、固形分濃度、すなわちバインダー含有量を高くすることが考えられるが、通常、固形分濃度を高くすると溶液粘度が上昇し、溶液の経時粘度安定性が悪くなるという問題がある。 Also, from the viewpoint of environmental protection, the use of polyvinyl acetal resin, which has excellent solubility in alcohol-based single solvents such as ethanol and propanol, without using aromatic solvents such as toluene and xylene, has increased. ing. From the viewpoint of environmental protection, as seen in the VOC regulations for automobiles, there are three major flows: high solidification, water purification, and powdering. In particular, high-solidification requires less capital investment than the other two, only uses less solvent and increases the solids concentration, and can be inferred and guaranteed from the conventional product. It has been broken. As a method for realizing high solidification using a polyvinyl acetal resin, it is conceivable to increase the solid content concentration, that is, the binder content. However, when the solid content concentration is increased, the viscosity of the solution increases and the aging of the solution increases. There is a problem that the viscosity stability deteriorates.
特許文献３には、カルボン酸変性ポリビニルアルコールと、エチレン変性度２０モルまでの変性ポリビニルアルコールの混合物による印刷性の向上に関する提案がなされている。しかしながら、近年の積層セラミックコンデンサの更なる小型化・高容量化に対応するためには、高い印刷性を保持しながら、環境保護の観点にも対応していくことが望まれる。 Patent Document 3 proposes an improvement in printability by a mixture of carboxylic acid-modified polyvinyl alcohol and a modified polyvinyl alcohol having an ethylene modification degree of up to 20 mol. However, in order to cope with further downsizing and higher capacity of the multilayer ceramic capacitor in recent years, it is desired to cope with the viewpoint of environmental protection while maintaining high printability.
また、低粘度化には、原料のポリビニルアルコールに、ケン化度の低いものを用いることが有効であることも知られている。特許文献４には、７０〜９６モル％のケン化度をもつポリビニルアルコールを原料としたポリビニルブチラール樹脂を含む印刷インク及び塗料が開示されている。しかし、このポリビニルブチラール樹脂を含む溶液では、残存するアセチル基の量を抑制することにより、低粘度化を達成することはできるが、チキソトロピー性に関しては充分なものではなく、印刷性は十分であるとはいえなかった。 It is also known that, in order to lower the viscosity, it is effective to use a raw material polyvinyl alcohol having a low saponification degree. Patent Document 4 discloses a printing ink and a paint containing a polyvinyl butyral resin made from polyvinyl alcohol having a saponification degree of 70 to 96 mol% as a raw material. However, in the solution containing this polyvinyl butyral resin, the viscosity can be reduced by suppressing the amount of remaining acetyl groups, but the thixotropic property is not sufficient, and the printability is sufficient. That wasn't true.
本発明は、上記現状に鑑み、低粘度でハイソリッド化が可能であり、かつ、チキソトロピー性に優れ、印刷時の糸引き、目詰まり及びニジミを抑制することが可能な変性ポリビニルアセタール樹脂、並びに、該変性ポリビニルアセタール樹脂を用いてなるセラミックグリーンシート用スラリー組成物及びセラミックグリーンシートを提供することを目的とする。 In view of the above situation, the present invention is a modified polyvinyl acetal resin that can be made into a high solid with low viscosity, has excellent thixotropy, and can suppress stringing, clogging, and blurring during printing, and An object of the present invention is to provide a ceramic green sheet slurry composition and a ceramic green sheet using the modified polyvinyl acetal resin.
本発明は、分子中にスルホン酸基を有し、かつ、主鎖中にα−オレフィン単位を有する変性ポリビニルアセタール樹脂であり、アセタール単位内にスルホン酸基を有し、前記α−オレフィン単位の含有量が２５〜５０モル％、前記スルホン酸基の含有量が０．１〜１０モル％、水酸基量が４０モル％以下である変性ポリビニルアセタール樹脂である。
以下に本発明を詳述する。
The present invention is a modified polyvinyl acetal resin having a sulfonic acid group in the molecule and an α-olefin unit in the main chain, having a sulfonic acid group in the acetal unit, A modified polyvinyl acetal resin having a content of 25 to 50 mol%, a content of the sulfonic acid group of 0.1 to 10 mol%, and a hydroxyl group content of 40 mol% or less.
The present invention is described in detail below.
本発明者らは、鋭意検討の結果、例えば、セラミックグリーンシート用スラリー組成物のバインダー樹脂として、分子中のアセタール単位内にスルホン酸基を有し、かつ、主鎖中にα−オレフィン単位を有し、α−オレフィン単位、スルホン酸基及び水酸基の含有量が所定の範囲内の変性ポリビニルアセタール樹脂を用いた場合、低粘度とチキソトロピー性とを有しつつ、印刷性にも優れるセラミックグリーンシート用スラリー組成物が得られることを見出し、本発明を完成させるに至った。 As a result of intensive studies, the present inventors have, for example, a sulfonic acid group in the acetal unit in the molecule and a α-olefin unit in the main chain as the binder resin of the slurry composition for ceramic green sheets. Ceramic green sheet having a low viscosity and thixotropy and having excellent printability when a modified polyvinyl acetal resin having an α-olefin unit, a sulfonic acid group and a hydroxyl group within a predetermined range is used. The present inventors have found that a slurry composition can be obtained and have completed the present invention.
本発明の変性ポリビニルアセタール樹脂は、主鎖中にα−オレフィン単位を有する。
上記α−オレフィン単位は、例えば、酢酸ビニルモノマーとエチレンとの共重合により主鎖中に含まれる構造となる。この場合、α−オレフィン単位は主鎖中にランダムに導入され、水酸基の水素結合性を、強固な結晶を形成する程度までではないものの、分子鎖同士が適度に会合性を有する程度に低下させることができる。その結果、スラリー組成物の粘度を低下させることができると解釈される。
変性ポリビニルアセタール樹脂は、エタノール：トルエンの混合溶媒や、エチルメチルケトンといった、本技術領域において汎用の溶媒に高い溶解性を示す。
The modified polyvinyl acetal resin of the present invention has an α-olefin unit in the main chain.
The α-olefin unit has a structure contained in the main chain by copolymerization of a vinyl acetate monomer and ethylene, for example. In this case, α-olefin units are randomly introduced into the main chain, and the hydrogen bonding properties of the hydroxyl groups are reduced to such an extent that the molecular chains have moderate associative properties, although not to the extent that they form strong crystals. be able to. As a result, it is interpreted that the viscosity of the slurry composition can be reduced.
The modified polyvinyl acetal resin exhibits high solubility in a general-purpose solvent such as a mixed solvent of ethanol: toluene and ethyl methyl ketone.
本発明の変性ポリビニルアセタール樹脂は、α−オレフィン単位の含有量の下限が２５モル％、上限が５０モル％である。
上記α−オレフィン単位の含有量が２５モル％未満であると、得られる変性ポリビニルアセタール樹脂の粘度が高くなりすぎ、充分なハイソリッド効果が得られない。また、上記α−オレフィン単位の含有量が５０モル％を超えると、樹脂の疎水性が強くなりすぎ、無機粉末の分散性が低下するため、印刷時の目詰まりの原因となることがある。なお、変性ポリビニルアセタール樹脂中のα−オレフィン単位の含有量は、変性ポリビニルアセタール樹脂の原料であるポリビニルアルコールに共重合させるα−オレフィンの量を制御することで調整することができる。上記α−オレフィン単位の含有量の好ましい下限は３０モル％、好ましい上限は４８モル％である。
In the modified polyvinyl acetal resin of the present invention, the lower limit of the content of α-olefin units is 25 mol%, and the upper limit is 50 mol%.
When the content of the α-olefin unit is less than 25 mol%, the viscosity of the resulting modified polyvinyl acetal resin becomes too high, and a sufficient high solid effect cannot be obtained. On the other hand, when the content of the α-olefin unit exceeds 50 mol%, the hydrophobicity of the resin becomes too strong and the dispersibility of the inorganic powder is lowered, which may cause clogging during printing. In addition, content of the alpha olefin unit in modified polyvinyl acetal resin can be adjusted by controlling the quantity of alpha olefin copolymerized with the polyvinyl alcohol which is the raw material of modified polyvinyl acetal resin. The minimum with preferable content of the said alpha olefin unit is 30 mol%, and a preferable upper limit is 48 mol%.
上記α−オレフィンとしては、例えば、エチレン、プロピレン、イソプロピレン、ブチレン、イソブチレン、ペンチレン、へキシレン、シクロヘキシレン、シクロヘキシルエチレン、シクロヘキシルプロピレンが挙げられる。なかでも、エチレンが好ましい。 Examples of the α-olefin include ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, hexylene, cyclohexylene, cyclohexylethylene, and cyclohexylpropylene. Of these, ethylene is preferable.
本発明の変性ポリビニルアセタール樹脂は、アセタール化度の好ましい下限が２２モル％である。
上記アセタール化度が２２モル％未満であると、得られる変性ポリビニルアセタール樹脂の溶剤溶解性が低下したり、ガラス転移温度が高くなり、充分な内部可塑効果が得られないため、セラミックグリーンシートの強度が低下することがある。また、内部電極となる導電ペースト等の被着体との接着性が低下するといった不具合が起こることがある。
上記アセタール化度のより好ましい下限は２５モル％、好ましい上限は５５モル％である。
なお、ここでいうアセタール化度とは、変性ポリビニルアセタール樹脂を構成する全単量体単位に対する、アセタール化されたビニルアルコール単位の割合を表し、該変性ポリビニルアセタール樹脂のＤＭＳＯ−ｄ６（ジメチルスルホキサイド）溶液を試料としてプロトンＮＭＲ測定を行い、得られたスペクトルから算出することができる。
In the modified polyvinyl acetal resin of the present invention, the preferable lower limit of the degree of acetalization is 22 mol%.
When the degree of acetalization is less than 22 mol%, the solvent solubility of the resulting modified polyvinyl acetal resin is lowered, the glass transition temperature is increased, and a sufficient internal plastic effect cannot be obtained. The strength may decrease. In addition, there may be a problem that adhesiveness with an adherend such as a conductive paste serving as an internal electrode is lowered.
The more preferable lower limit of the degree of acetalization is 25 mol%, and the preferable upper limit is 55 mol%.
The degree of acetalization here refers to the ratio of acetalized vinyl alcohol units to the total monomer units constituting the modified polyvinyl acetal resin, and DMSO-d 6 (dimethylsulfone) of the modified polyvinyl acetal resin. It can be calculated from the spectrum obtained by carrying out proton NMR measurement using a (xoxide) solution as a sample.
本発明の変性ポリビニルアセタール樹脂は、分子中にスルホン酸基を有する。なお、上記スルホン酸基は、スルホン酸基又はその塩を意味する。また、主鎖の途中にスルホン酸基を有する場合のほか、アセタール単位内にスルホン酸基を有する場合も含む。 The modified polyvinyl acetal resin of the present invention has a sulfonic acid group in the molecule. The sulfonic acid group means a sulfonic acid group or a salt thereof. In addition to the case of having a sulfonic acid group in the middle of the main chain, the case of having a sulfonic acid group in the acetal unit is also included.
本発明の変性ポリビニルアセタール樹脂は、アセタール単位内にスルホン酸基を有することが好ましい。これにより、チキソトロピー性に優れ、印刷時の糸引き、目詰まり及びニジミを抑制することが可能となる。 The modified polyvinyl acetal resin of the present invention preferably has a sulfonic acid group in the acetal unit. Thereby, it is excellent in thixotropy and can suppress stringing, clogging, and blurring during printing.
本発明の変性ポリビニルアセタール樹脂は、芳香族系置換基を有することが好ましく、上記アセタール単位内に、芳香族系置換基とともに、スルホン酸基を有することが好ましい。
これにより、適度な疎水性が付与され、スルホン酸基の含有量が高い場合でも、溶媒への溶解性を保つことができる。また、変性ポリビニルアセタールの主鎖に剛直性を持たせることにより、分子間の絡まりを抑制し、高速のせん断速度の場合に樹脂溶液の粘度を下げ、チキソトロピー性を向上させることが可能となる。
The modified polyvinyl acetal resin of the present invention preferably has an aromatic substituent, and preferably has a sulfonic acid group together with the aromatic substituent in the acetal unit.
Thereby, moderate hydrophobicity is imparted and solubility in a solvent can be maintained even when the content of sulfonic acid groups is high. Further, by imparting rigidity to the main chain of the modified polyvinyl acetal, it is possible to suppress entanglement between molecules, lower the viscosity of the resin solution at a high shear rate, and improve thixotropy.
本発明の変性ポリビニルアセタール樹脂において、上記スルホン酸基の含有量は０．１〜１０モル％である。２〜８モル％であることがより好ましい。０．１モル％未満であると、スルホン酸基の量が少なすぎるため、チクソ性が充分に改善されず、糸引きやニジミを抑制できず、１０モル％を超えると、得られる変性ポリビニルアセタール樹脂の極性が高くなりすぎ、溶剤への溶解性が低下した結果、未溶解樹脂が多数性生成し、得られるセラミックペーストの印刷性が悪化する。
なお、上記スルホン酸基の含有量とは、変性ポリビニルアセタール樹脂を構成する全単量体単位に対する、アセタール化されたビニルアルコール単位の割合を表し、該変性ポリビニルアセタール樹脂のＤＭＳＯ−ｄ６（ジメチルスルホキサイド）溶液を試料として１３Ｃ−ＮＭＲ測定を行い、得られたスペクトルのスルホン酸基に直接結合した炭素と主鎖部位（４１−４５ｐｐｍ）の積分比から算出することができる。
In the modified polyvinyl acetal resin of the present invention, the content of the sulfonic acid group is 0.1 to 10 mol%. It is more preferable that it is 2-8 mol%. If the amount is less than 0.1 mol%, the amount of the sulfonic acid group is too small, so that thixotropy is not sufficiently improved, and stringing and blurring cannot be suppressed. If the amount exceeds 10 mol%, the resulting modified polyvinyl acetal The polarity of the resin becomes too high and the solubility in the solvent is reduced. As a result, a large number of undissolved resins are formed, and the printability of the resulting ceramic paste is deteriorated.
The content of the sulfonic acid group represents a ratio of vinyl alcohol units acetalized to all monomer units constituting the modified polyvinyl acetal resin, and DMSO-d 6 (dimethyl) of the modified polyvinyl acetal resin. 13 C-NMR measurement is carried out using a sulfoxide) solution as a sample, and it can be calculated from the integral ratio of the carbon directly bonded to the sulfonic acid group of the spectrum obtained and the main chain site (41-45 ppm).
本発明の変性ポリビニルアセタール樹脂は、水酸基量が４０モル％以下である。上記水酸基量が４０モル％を超えると、変性ポリビニルアセタール樹脂の溶剤への溶解性が低下し、未溶解樹脂が多数生成することから、印刷時に目詰まりの原因となる悪化する。上記水酸基量は２５〜３５モル％であることが好ましい。 The modified polyvinyl acetal resin of the present invention has a hydroxyl group content of 40 mol% or less. When the amount of the hydroxyl group exceeds 40 mol%, the solubility of the modified polyvinyl acetal resin in the solvent is reduced, and a large number of undissolved resins are produced, resulting in deterioration that causes clogging during printing. The amount of the hydroxyl group is preferably 25 to 35 mol%.
本発明の変性ポリビニルアセタール樹脂は、重合度が２００〜３５００であることが好ましい。上記重合度が２００未満であると、セラミックグリーンシートとした際に、充分な強度を保てない場合がある。上記重合度が３５００を超えると、セラミックグリーンシート用スラリー組成物の粘度が高くなり過ぎるために、セラミック粉末の分散性が悪く、均質なスラリーが得られない場合がある。より好ましくは１０００〜３０００、更に好ましくは１５００〜２４００である。 The modified polyvinyl acetal resin of the present invention preferably has a polymerization degree of 200-3500. When the degree of polymerization is less than 200, sufficient strength may not be maintained when a ceramic green sheet is obtained. When the degree of polymerization exceeds 3500, the viscosity of the slurry composition for ceramic green sheets becomes too high, so that the dispersibility of the ceramic powder is poor and a homogeneous slurry may not be obtained. More preferably, it is 1000-3000, More preferably, it is 1500-2400.
本発明の変性ポリビニルアセタール樹脂は、α−オレフィン−ビニルアルコール共重合体を原料とし、主鎖中にα−オレフィン単位を特定の割合で有するα−オレフィン−ビニルアルコール共重合体をアセタール化することで製造することができる。
また、アセタール化において、スルホン酸基を有するアルデヒドを用いることで、分子中にスルホン酸基を有する変性ポリビニルアセタール樹脂を製造することができる。
The modified polyvinyl acetal resin of the present invention uses an α-olefin-vinyl alcohol copolymer as a raw material, and acetalizes an α-olefin-vinyl alcohol copolymer having an α-olefin unit in a specific ratio in the main chain. Can be manufactured.
Moreover, the modified polyvinyl acetal resin which has a sulfonic acid group in a molecule | numerator can be manufactured by using the aldehyde which has a sulfonic acid group in acetalization.
上記α−オレフィン−ビニルアルコール共重合体は、ケン化度が８０モル％以上のものを用いることが好ましく、９０モル以上のものを用いることがより好ましい。
上記ケン化度が８０モル％未満であると、アセタール化が充分に進行せず、内部可塑効果が低下するため、得られるセラミックグリーンシートの強度が低下することがある。
なお、本明細書において、α−オレフィン−ビニルアルコール共重合体のケン化度とは、エチレン単位を除く、酢酸ビニル単位のうち、ビニルアルコール単位に変換された割合を指す。 なお、ケン化度は、エチレンーポリビニルアルコール共重合体のＤＭＳＯ−ｄ６（ジメチルスルホキサイド） ２重量％溶液を試料として、１Ｈ−ＮＭＲ測定を行い、得られたスペクトルの積分比から算出することができる
The α-olefin-vinyl alcohol copolymer preferably has a saponification degree of 80 mol% or more, and more preferably 90 mol or more.
When the saponification degree is less than 80 mol%, acetalization does not proceed sufficiently and the internal plastic effect is lowered, so that the strength of the obtained ceramic green sheet may be lowered.
In the present specification, the saponification degree of the α-olefin-vinyl alcohol copolymer refers to the ratio of vinyl acetate units converted to vinyl alcohol units excluding ethylene units. The degree of saponification was calculated from the integral ratio of the spectrum obtained by performing 1 H-NMR measurement using a 2 wt% solution of ethylene-polyvinyl alcohol copolymer in DMSO-d 6 (dimethyl sulfoxide) as a sample. can do
上記アセタール化は、有機溶媒中で行うことが好ましい。
上記有機溶媒としては、例えば、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、ｔｅｒｔ−ブタノール等のアルコール系有機溶剤；キシレン、トルエン、エチルベンゼン、安息香酸メチル等の芳香族有機溶剤；酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル、プロピオン酸エチル、酪酸メチル、酪酸エチル、アセト酢酸メチル、アセト酢酸エチル等の脂肪族エステル系溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、メチルシクロヘキサノン、ベンゾフェノン、アセトフェノン等のケトン系溶剤；ヘキサン、ペンタン、オクタン、シクロヘキサン、デカン等の低級パラフィン系溶剤；ジエチルエーテル、テトラヒドロフラン、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコールジエチルエーテル等のエーテル系溶剤；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルテセトアミド、Ｎ−メチルピロリドン、アセトアニリド等のアミド系溶剤、アンモニア、トリメチルアミン、トリエチルアミン、ｎ−ブチルアミン、ジｎ−ブチルアミン、トリｎ−ブチルアミン、アニリン、Ｎ−メチルアニリン、Ｎ，Ｎ−ジメチルアニリン、ピリジン等のアミン系溶剤等が挙げられる。これらは、単体で用いることもできるし、２種以上の溶媒を混合で用いることもできる。これらのなかでも、樹脂に対する溶解性および、精製時の簡易性の観点から、エタノール、ｎ−プロパノール、イソプロパノール、テトラヒドロフランが特に好ましい。
The acetalization is preferably performed in an organic solvent.
Examples of the organic solvent include alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol; aromatic organic solvents such as xylene, toluene, ethylbenzene, and methyl benzoate; Aliphatic ester solvents such as ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl acetoacetate, ethyl acetoacetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, benzophenone Ketone solvents such as acetophenone; lower paraffin solvents such as hexane, pentane, octane, cyclohexane, decane; diethyl ether, tetrahydrofuran, ethylene glycol dimethyl Ether solvents such as ether, ethylene glycol diethyl ether, propylene glycol diethyl ether; amide solvents such as N, N-dimethylformamide, N, N-dimethyltecetamide, N-methylpyrrolidone, acetanilide, ammonia, trimethylamine, triethylamine, Examples thereof include amine solvents such as n-butylamine, di-n-butylamine, tri-n-butylamine, aniline, N-methylaniline, N, N-dimethylaniline, and pyridine. These can be used alone or in a mixture of two or more solvents. Among these, ethanol, n-propanol, isopropanol, and tetrahydrofuran are particularly preferable from the viewpoints of solubility in the resin and simplicity during purification.
上記アセタール化は、酸触媒の存在下において行うことが好ましい。
上記酸触媒は特に限定されず、塩酸等のハロゲン化水素や、硝酸、硫酸等の鉱酸や、ギ酸、酢酸、プロピオン酸等のカルボン酸や、メタンスルホン酸、 エタンスルホン酸、ベンゼンスルホン酸、パラトルエンスルホン酸等のスルホン酸や、リン酸等が挙げられる。これらの酸触媒は、単独で用いられても よく、２種以上の化合物を併用してもよい。なかでも、塩酸、硝酸、硫酸が好ましく、塩酸が特に好ましい。
The acetalization is preferably performed in the presence of an acid catalyst.
The acid catalyst is not particularly limited, hydrogen halides such as hydrochloric acid, mineral acids such as nitric acid and sulfuric acid, carboxylic acids such as formic acid, acetic acid and propionic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, Examples thereof include sulfonic acids such as paratoluenesulfonic acid, phosphoric acid and the like. These acid catalysts may be used alone or in combination of two or more compounds. Of these, hydrochloric acid, nitric acid and sulfuric acid are preferable, and hydrochloric acid is particularly preferable.
上記アセタール化に用いられるアルデヒドとしては、スルホン酸基を有するアルデヒドを用いることが好ましく、具体的には例えば、スルホン酸基と芳香族系置換基とを有するアルデヒドと、スルホン酸基を有しないアルデヒドとを組み合わせて用いることが好ましい。 As the aldehyde used in the acetalization, an aldehyde having a sulfonic acid group is preferably used. Specifically, for example, an aldehyde having a sulfonic acid group and an aromatic substituent, and an aldehyde having no sulfonic acid group Are preferably used in combination.
上記スルホン酸基と芳香族系置換基とを有するアルデヒドとしては、例えば、下記式（１）〜（３）に示す構造を有するアルデヒド等が挙げられる。なお、上記スルホン酸基は、アルデヒド中に１つ含まれていてもよく、複数含まれていてもよい。 Examples of the aldehyde having the sulfonic acid group and the aromatic substituent include aldehydes having structures represented by the following formulas (1) to (3). In addition, the said sulfonic acid group may be contained in the aldehyde, and multiple may be contained.
上記式（１）〜（３）において、ＸはＯ、Ｎ、Ｓを表し、ＭはＨ、Ｎａ、Ｋを表す。
また、上記スルホン酸基は、アルデヒド基に対して、２位、３位、４位のいずれに導入されていてもよい。
上記スルホン酸基と芳香族系置換基とを有するアルデヒドのなかでも、ｐ−ホルミルベンゼンスルホン酸ナトリウム、４−ホルミルベンゼン−１，３−ジスルホン酸二ナトリウム、が好ましく、４−ホルミルベンゼン−１，３−ジスルホン酸二ナトリウムがより好ましい。
In the above formulas (1) to (3), X represents O, N, S, and M represents H, Na, K.
The sulfonic acid group may be introduced at any of the 2-position, 3-position, and 4-position with respect to the aldehyde group.
Of the aldehydes having a sulfonic acid group and an aromatic substituent, sodium p-formylbenzenesulfonate and disodium 4-formylbenzene-1,3-disulfonate are preferred, and 4-formylbenzene-1, More preferred is disodium 3-disulfonate.
上記スルホン酸基を有しないアルデヒドとしては、炭素数１〜１０の鎖状脂肪族基、環状脂肪族基又は芳香族基を有するアルデヒドが挙げられる。これらのアルデヒドとしては、従来公知のアルデヒドを使用できる。上記アセタール化反応に用いられるアルデヒドは、特に限定されるものではなく、例えば、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ｎ−ブチルアルデヒド、イソブチルアルデヒド、ｎ−バレルアルデヒド、ｎ−ヘキシルアルデヒド、２−エチルブチルアルデヒド、２−エチルヘキシルアルデヒド、ｎ−ヘプチルアルデヒド、ｎ−オクテルアルデヒド、ｎ−ノニルアルデヒド、ｎ−デシルアルデヒド、アミルアルデヒド、等の脂肪族アルデヒド、ベンズアルデヒド、シンナムアルデヒド、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の芳香族アルデヒド等が挙げられる。これらのアルデヒドは、１種を単独で使用してもよく、２種以上を併用してもよい。上記アルデヒドとしては、なかでも、アセタール化反応性に優れ、生成する樹脂に十分な内部可塑効果をもたらし、結果として良好な柔軟性を付与することができるブチルアルデヒド、２−エチルヘキシルアルデヒド、ｎ−ノニルアルデヒドが好ましく、ブチルアルデヒドがより好ましい。 Examples of the aldehyde having no sulfonic acid group include aldehydes having a chain aliphatic group having 1 to 10 carbon atoms, a cyclic aliphatic group, or an aromatic group. Conventionally known aldehydes can be used as these aldehydes. The aldehyde used in the acetalization reaction is not particularly limited. For example, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde Aliphatic aldehydes such as 2-ethylhexylaldehyde, n-heptylaldehyde, n-octaldehyde, n-nonylaldehyde, n-decylaldehyde, amylaldehyde, benzaldehyde, cinnamaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, β-phenylpropionaldehyde, etc. Aromatic aldehydes, and the like. These aldehydes may be used alone or in combination of two or more. Among these aldehydes, butyraldehyde, 2-ethylhexyl aldehyde, n-nonyl, which are excellent in acetalization reactivity and provide a sufficient internal plastic effect to the resulting resin, and as a result, can impart good flexibility. Aldehydes are preferred and butyraldehyde is more preferred.
上記アルデヒドの添加量としては、目的とする変性ポリビニルアセタール樹脂のスルホン酸基変性量や、アセタール化度にあわせて適宜設定すればよい。特に、α−オレフィン−ビニルアルコール共重合体１００モル％に対して、３０〜７５モル％、好ましくは４０〜６５モル％とすると、アセタール化反応が効率よく行われ、未反応のアルデヒドも除去しやすいため好ましい。
また、スルホン酸基と芳香族系置換基とを有するアルデヒドと、スルホン酸基を有しないアルデヒドとを組み合わせて用いる場合は、スルホン酸基と芳香族系置換基とを有するアルデヒドをアルデヒド全体の２０〜５０モル％とすることが好ましい。
What is necessary is just to set suitably as the addition amount of the said aldehyde according to the sulfonic-acid group modification amount of the target modified polyvinyl acetal resin, and the acetalization degree. In particular, when the content is 30 to 75 mol%, preferably 40 to 65 mol%, based on 100 mol% of the α-olefin-vinyl alcohol copolymer, the acetalization reaction is efficiently performed and unreacted aldehyde is also removed. It is preferable because it is easy.
When an aldehyde having a sulfonic acid group and an aromatic substituent is used in combination with an aldehyde not having a sulfonic acid group, the aldehyde having a sulfonic acid group and an aromatic substituent is used as the aldehyde of the entire aldehyde. It is preferable to set it to -50 mol%.
本発明の変性ポリビニルアセタール樹脂に、有機溶剤、セラミック粉末等を添加することでセラミックグリーンシート用スラリー組成物が得られる。このようなセラミックグリーンシート用スラリー組成物もまた本発明の一つである。 A slurry composition for a ceramic green sheet can be obtained by adding an organic solvent, ceramic powder or the like to the modified polyvinyl acetal resin of the present invention. Such a slurry composition for ceramic green sheets is also one aspect of the present invention.
上記セラミック粉末としては、セラミックの製造に使用される金属または非金属の酸化物もしくは非酸化物の粉末が挙げられる。また、これらの粉末の組成は単一組成、化合物の状態のものを単独または混合して使用しても差し支えない。なお、金属の酸化物または非酸化物の構成元素はカチオンまたはアニオンともに単元素でも複数の元素から成り立っていてもよく、さらに酸化物または非酸化物の特性を改良するために加えられる添加物を含んでいてもよい。具体的には、Ｌｉ、Ｋ、Ｍｇ、Ｂ、Ａｌ、Ｓｉ、Ｃｕ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ｃｄ、Ｇａ、Ｉｎ、Ｙ、ランタノイド、アクチノイド、Ｔｉ、Ｚｒ、Ｈｆ、Ｂｉ、Ｖ、Ｎｂ、Ｔａ、Ｗ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ等の酸化物、炭化物、窒化物、ホウ化物、硫化物等が挙げられる。
また、通常複酸化物と称される複数の金属元素を含む酸化物粉末の具体的なものを結晶構造から分類すると、ペロブスカイト型構造をとるものとしてＮａＮｂＯ３、ＳｒＺｒＯ３、ＰｂＺｒＯ３、ＳｒＴｉＯ３、ＢａＺｒＯ３、ＰｂＴｉＯ３、ＢａＴｉＯ３等が、スピネル型構造をとるものとしてＭｇＡｌ２Ｏ４、ＺｎＡｌ２Ｏ４、ＣｏＡｌ２Ｏ４、ＮｉＡｌ２Ｏ４、ＭｇＦｅ２Ｏ４等が、イルメナイト型構造をとるものとしてはＭｇＴｉＯ３、ＭｎＴｉＯ３、ＦｅＴｉＯ３等が、ガーネット型構造をとるものとしてはＧｄＧａ５Ｏ１２、Ｙ６Ｆｅ５Ｏ１２等が挙げられる。 この中でも、本願の変性ポリビニルアセタール樹脂は、ＢａＴｉＯ３の粉末と混合したセラミックグリーンシートに対し、高い特性を示す。
Examples of the ceramic powder include metal or nonmetal oxide or nonoxide powder used in the production of ceramics. Further, these powders may be used in a single composition or in a compound state alone or in combination. The constituent element of the metal oxide or non-oxide may be composed of a single element or a plurality of elements, both cation and anion, and further contains additives added to improve the characteristics of the oxide or non-oxide. May be included. Specifically, Li, K, Mg, B, Al, Si, Cu, Ca, Sr, Ba, Zn, Cd, Ga, In, Y, lanthanoid, actinoid, Ti, Zr, Hf, Bi, V, Nb , Ta, W, Mn, Fe, Co, Ni, and other oxides, carbides, nitrides, borides, sulfides, and the like.
Moreover, usually when classified concrete things a crystal structure of an oxide powder containing a plurality of metal elements referred to as double oxides, NaNbO 3, SrZrO 3, PbZrO 3, SrTiO 3 as taking a perovskite structure, BaZrO 3 , PbTiO 3 , BaTiO 3, etc. take a spinel structure, and MgAl 2 O 4 , ZnAl 2 O 4 , CoAl 2 O 4 , NiAl 2 O 4 , MgFe 2 O 4, etc. take an ilmenite type structure. the ones MgTiO 3, MnTiO 3, FeTiO 3 etc., as to take a garnet structure can be mentioned GdGa 5 O 12, Y 6 Fe 5 O 12 and the like. Among these, the modified polyvinyl acetal resin of the present application exhibits high characteristics with respect to the ceramic green sheet mixed with the BaTiO 3 powder.
上記セラミック粉末の平均粒子径は、特に限定されるものではないが、例えば、薄層セラミックグリーンシート（厚さ５μｍ以下）の作製用としては、０．５μｍ以下であることが好ましい。 The average particle diameter of the ceramic powder is not particularly limited. For example, for producing a thin ceramic green sheet (thickness of 5 μm or less), it is preferably 0.5 μm or less.
本発明のスラリー組成物では、本発明の効果を損なわない範囲で、本発明の変性ポリビニルアセタール樹脂以外のポリビニルアセタール樹脂や、アクリル樹脂、エチルセルロース等の他の樹脂を含有していてもよい。しかし、このような場合、全バインダー樹脂に対する本発明の変性ポリビニルアセタール樹脂の含有量が５０重量％以上である必要がある。 The slurry composition of the present invention may contain other resins such as a polyvinyl acetal resin other than the modified polyvinyl acetal resin of the present invention, an acrylic resin, and ethyl cellulose as long as the effects of the present invention are not impaired. However, in such a case, the content of the modified polyvinyl acetal resin of the present invention with respect to the total binder resin needs to be 50% by weight or more.
本発明のスラリー組成物は、セラミック粉末及び無機分散用有機溶剤を含有する無機分散液と、本発明の変性ポリビニルアセタール樹脂及び樹脂溶液用有機溶剤を含有する樹脂溶液とを別々に作製した後、両者を混合する方法で作製することが好ましい。 The slurry composition of the present invention was prepared by separately preparing an inorganic dispersion containing ceramic powder and an organic solvent for inorganic dispersion, and a resin solution containing the modified polyvinyl acetal resin of the present invention and an organic solvent for resin solution, It is preferable to produce by the method of mixing both.
上記無機分散用有機溶剤及び樹脂溶液用有機溶剤としては特に限定されず、一般的にスラリー組成物に用いられる有機溶剤を使用することができるが、例えば、アセトン、メチルエチルケトン、ジプロピルケトン、ジイソブチルケトン等のケトン類、メタノール、エタノール、イソプロパノール、ブタノール等のアルコール類、トルエン、キシレン等の芳香族炭化水素類、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸ブチル、ブタン酸メチル、ブタン酸エチル、ブタン酸ブチル、ペンタン酸メチル、ペンタン酸エチル、ペンタン酸ブチル、ヘキサン酸メチル、ヘキサン酸エチル、ヘキサン酸ブチル、酢酸２−エチルヘキシル、酪酸２−エチルヘキシル等のエステル類、テルピネオール、ジヒドロテルピネオール、テルピネオールアセテート、ジヒドロテルピネオールアセテート等のテルピネオール及びその誘導体等が挙げられる。これらの有機溶剤は単独で用いられてもよく、２種以上が併用されてもよい。 The organic solvent for inorganic dispersion and the organic solvent for resin solution are not particularly limited, and organic solvents generally used in slurry compositions can be used. For example, acetone, methyl ethyl ketone, dipropyl ketone, diisobutyl ketone Ketones such as methanol, ethanol, isopropanol, butanol, aromatic hydrocarbons such as toluene, xylene, methyl propionate, ethyl propionate, butyl propionate, methyl butanoate, ethyl butanoate, butanoic acid Esters such as butyl, methyl pentanoate, ethyl pentanoate, butyl pentanoate, methyl hexanoate, ethyl hexanoate, butyl hexanoate, 2-ethylhexyl acetate, 2-ethylhexyl butyrate, terpineol, dihydroterpineol, terpineol Seteto, terpineol and its derivatives such as dihydro terpineol acetate, and the like. These organic solvents may be used independently and 2 or more types may be used together.
上記無機分散用有機溶剤及び樹脂溶液用有機溶剤としては、特にエタノール及びトルエンからなる混合溶媒を用いることが好ましい。上記混合溶媒を用いることによって、スラリー組成物の分散性を大幅に向上させることができる。これは、エタノールがポリビニルアセタール樹脂の凝集防止に寄与するのに対して、トルエンが分散剤の無機粉末表面への付着に寄与し、これらの相乗効果によってスラリー組成物の分散性が向上するためであると考えられる。 As the organic solvent for inorganic dispersion and the organic solvent for resin solution, it is particularly preferable to use a mixed solvent composed of ethanol and toluene. By using the mixed solvent, the dispersibility of the slurry composition can be greatly improved. This is because ethanol contributes to the prevention of aggregation of the polyvinyl acetal resin, while toluene contributes to the adhesion of the dispersant to the inorganic powder surface, and the synergistic effect of these improves the dispersibility of the slurry composition. It is believed that there is.
上記混合溶媒を用いる場合における上記エタノールとトルエンとの混合比については、５：５〜２：８とすることが好ましい。上記範囲内とすることで、スラリー組成物の分散性を向上させることが可能となる。 When the mixed solvent is used, the mixing ratio of ethanol and toluene is preferably 5: 5 to 2: 8. By setting it within the above range, the dispersibility of the slurry composition can be improved.
上記無機分散液を作製する工程における上記無機分散用有機溶剤の添加量の好ましい下限は無機粉末１００重量部に対して２０重量部、好ましい上限は６０重量部である。上記無機分散用有機溶剤の添加量が２０重量部未満であると、分散液の粘度が高くなり、無機粉末の動きが制限され充分な分散性が得られないことがあり、６０重量部を超えると、分散液の無機粉末濃度が低くなり、無機粉末同士の衝突回数が減るため充分な分散性が得られないことがある。
また、上記樹脂溶液を作製する工程における上記樹脂溶液用有機溶剤の添加量の好ましい下限は無機粉末１００重量部に対して７０重量部、好ましい上限は１３０重量部である。上記樹脂溶液用有機溶剤の添加量が７０重量部未満であると、所望の粘度に調整することが困難となり、塗工性が低下することがあり、１３０重量部を超えると、無機粉末濃度が低くなり、乾燥後のグリーンシートが一様にならないことがある。
より好ましい下限は９０重量部、より好ましい上限は１１０重量部である。
The preferable lower limit of the amount of the inorganic dispersion organic solvent added in the step of preparing the inorganic dispersion is 20 parts by weight with respect to 100 parts by weight of the inorganic powder, and the preferable upper limit is 60 parts by weight. When the added amount of the organic solvent for inorganic dispersion is less than 20 parts by weight, the viscosity of the dispersion becomes high, the movement of the inorganic powder is restricted, and sufficient dispersibility may not be obtained, and it exceeds 60 parts by weight. If the concentration of the inorganic powder in the dispersion is low and the number of collisions between the inorganic powders is reduced, sufficient dispersibility may not be obtained.
Moreover, the preferable minimum of the addition amount of the said organic solvent for resin solutions in the process of producing the said resin solution is 70 weight part with respect to 100 weight part of inorganic powder, and a preferable upper limit is 130 weight part. When the addition amount of the organic solvent for the resin solution is less than 70 parts by weight, it may be difficult to adjust to a desired viscosity and the coating property may be deteriorated. The green sheet after drying may not be uniform.
A more preferred lower limit is 90 parts by weight, and a more preferred upper limit is 110 parts by weight.
本発明のセラミックグリーンシート用スラリー組成物を用いてなるセラミックグリーンシートもまた本発明の１つである。
本発明のセラミックグリーンシートの製造方法としては、例えば、本発明のセラミックグリーンシート用スラリー組成物を、離型処理したポリエステルフィルム上に、乾燥後の厚みが適当になるように塗工し常温で１時間風乾する。次いで、熱風乾燥機を用いて８０℃で３時間乾燥させる。続いて１２０℃で２時間乾燥させる方法等が挙げられる。
A ceramic green sheet using the slurry composition for a ceramic green sheet of the present invention is also one aspect of the present invention.
As a method for producing the ceramic green sheet of the present invention, for example, the slurry composition for a ceramic green sheet of the present invention is applied on a release-treated polyester film so that the thickness after drying is appropriate, and at room temperature. Air dry for 1 hour. Subsequently, it is made to dry at 80 degreeC for 3 hours using a hot air dryer. Then, the method of drying at 120 degreeC for 2 hours, etc. are mentioned.
本発明によれば、低粘度でハイソリッド化が可能であり、かつ、チキソトロピー性に優れ、印刷時の糸引き、目詰まり及びニジミを抑制することが可能な変性ポリビニルアセタール樹脂、並びに、該変性ポリビニルアセタール樹脂を用いてなるセラミックグリーンシート用スラリー組成物及びセラミックグリーンシートを提供できる。 According to the present invention, a modified polyvinyl acetal resin that can be made into a high solid with a low viscosity, has excellent thixotropy, and can suppress stringing, clogging, and blurring during printing, and the modification The slurry composition for ceramic green sheets and ceramic green sheet which use a polyvinyl acetal resin can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１）
＜変性ポリビニルアセタール樹脂の製造＞
エチレン含有量４８．０モル％、ケン化度９９．０％であり、主鎖の構成単位として、エチレンをランダムに有するエチレン−ビニルアルコール共重合体５０ｇをメタノール２００ｍＬに加え、６０℃の温度に加熱した。これに濃度２．０ｍｏｌ／Ｌの塩酸水溶液２０ｇとｎ−ブチルアルデヒド２４．８ｇ、４−ホルミルベンゼン−１，３−ジスルホン酸二ナトリウム（以下、構造Ａとする）１０．４ｇとを添加し、回転数２００ｒｐｍで３時間攪拌させた。このとき、エチレン−ビニルアルコール共重合体は反応が進行するにしたがって次第に溶解し、やがて均一な溶液が得られる。その後、炭酸ナトリウム８．２ｇを水３０ｇに溶解させたものを加え、中和を行った。
反応液を５℃に冷却した水１０００ｍＬ撹拌下滴下し、析出物を生成させた。このまま温度を１時間かけて４０℃まで上昇させ、４０℃で２時間攪拌した。生成した樹脂を濾取し、流水で３時間洗浄し、余剰の塩や未反応のアルデヒドを取り除いた。析出物を５０℃、５０ｍｍＨｇ条件下で４８時間真空乾燥を行い、変性ポリビニルアセタール樹脂を得た。
Example 1
<Manufacture of modified polyvinyl acetal resin>
An ethylene content of 48.0 mol%, a saponification degree of 99.0%, and 50 g of an ethylene-vinyl alcohol copolymer randomly containing ethylene as a main chain constituent unit are added to 200 mL of methanol. Heated. To this, 20 g of a 2.0 mol / L hydrochloric acid aqueous solution, 24.8 g of n-butyraldehyde, and 10.4 g of disodium 4-formylbenzene-1,3-disulfonate (hereinafter referred to as structure A) were added, The mixture was stirred at a rotation speed of 200 rpm for 3 hours. At this time, the ethylene-vinyl alcohol copolymer gradually dissolves as the reaction proceeds, and eventually a uniform solution is obtained. Thereafter, 8.2 g of sodium carbonate dissolved in 30 g of water was added for neutralization.
The reaction solution was added dropwise with stirring to 1000 mL of water cooled to 5 ° C. to produce a precipitate. In this state, the temperature was raised to 40 ° C. over 1 hour and stirred at 40 ° C. for 2 hours. The produced resin was collected by filtration and washed with running water for 3 hours to remove excess salt and unreacted aldehyde. The precipitate was vacuum dried for 48 hours under conditions of 50 ° C. and 50 mmHg to obtain a modified polyvinyl acetal resin.
次に、この変性ポリビニルブチラール樹脂を、ＤＭＳＯ−ｄ６（ジメチルスルホキサイド）に溶解させて、１３Ｃ−ＮＭＲスペクトルの測定を行ない、変性ポリビニルブチラール樹脂の組成及びブチラール化度を算出したところ、エチレン成分の含有量が４８．０モル％、ケン化度１．０モル％、水酸基量２５．２モル％、スルホン酸基含有量２．６モル％、ブチラール化度が２３．２モル％であった。 Next, when this modified polyvinyl butyral resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), the 13 C-NMR spectrum was measured, and the composition of the modified polyvinyl butyral resin and the degree of butyralization were calculated. The ethylene component content is 48.0 mol%, the saponification degree is 1.0 mol%, the hydroxyl group amount is 25.2 mol%, the sulfonic acid group content is 2.6 mol%, and the butyralization degree is 23.2 mol%. there were.
（セラミックペーストの作製）
得られた変性ポリビニルアセタール樹脂４．２ｇ、チタン酸バリウム（堺化学工業社製 商品名「ＢＴ−０３」、平均粒子径：０．３μｍ）５０ｇ並びにα−テルピネオール４５．８ｇを混合し、ボールミルを用いて４８時間混練してセラミックペーストを得た。
(Production of ceramic paste)
4.2 g of the obtained modified polyvinyl acetal resin, 50 g of barium titanate (trade name “BT-03” manufactured by Sakai Chemical Industry Co., Ltd., average particle size: 0.3 μm) and 45.8 g of α-terpineol were mixed, and a ball mill was mixed. And kneaded for 48 hours to obtain a ceramic paste.
（実施例２〜８、比較例２〜７）
エチレン含有量、ケン化度、スルホン酸アルデヒドの種類（スルホン酸アルデヒドとして、ｐ−ホルミルベンゼンスルホン酸ナトリウムを用いた場合、構造Ｂとした）、スルホン酸基含有量、ブチラール化度を表１に示したように変更したこと以外は実施例１と同様にして、変性ポリビニルアセタール樹脂、スラリー組成物を製造した。
(Examples 2-8, Comparative Examples 2-7)
Table 1 shows the ethylene content, the degree of saponification, the type of sulfonic acid aldehyde (when p-formylbenzene sodium sulfonate is used as the sulfonic acid aldehyde, the structure B), the content of sulfonic acid group, and the degree of butyralization. A modified polyvinyl acetal resin and a slurry composition were produced in the same manner as in Example 1 except that the changes were made as shown.
（比較例１）
実施例１の＜変性ポリビニルアセタール樹脂の製造＞において、４−ホルミルベンゼン−１，３−ジスルホン酸二ナトリウム１０．４ｇを添加しなかった以外は、実施例１と同様にして変性ポリビニルアセタール樹脂、スラリー組成物を製造した。
(Comparative Example 1)
In <Manufacture of modified polyvinyl acetal resin> in Example 1, modified polyvinyl acetal resin in the same manner as in Example 1 except that 10.4 g of disodium 4-formylbenzene-1,3-disulfonate was not added, A slurry composition was prepared.
＜評価＞
実施例及び比較例で得られた変性ポリビニルアセタール樹脂、スラリー組成物について以下の評価を行った。結果を表１に示した。
<Evaluation>
The following evaluation was performed about the modified polyvinyl acetal resin and slurry composition obtained by the Example and the comparative example. The results are shown in Table 1.
（スラリー組成物の粘度測定）
得られたスラリー組成物の回転速度が１（ｓ−１）の時点及び１００（ｓ−１）の時点での粘度を、回転式レオメータ（Ｂｏｌｉｎ社製、商品名「Ｇｅｍｉｎｉ １５０」）を用いて測定した。なお、上記粘度の測定は、直径４０ｍｍ、角度１°のコーンプレートを使用し、２５℃の温度条件下にて回転速度を０．１（ｓ−１）から１００（ｓ−１）まで上昇させて行った。
(Measurement of viscosity of slurry composition)
The viscosity at the time when the rotational speed of the obtained slurry composition was 1 (s −1 ) and 100 (s −1 ) was measured using a rotary rheometer (manufactured by Bolin, trade name “Gemini 150”). It was measured. The viscosity is measured by using a cone plate with a diameter of 40 mm and an angle of 1 °, and increasing the rotational speed from 0.1 (s −1 ) to 100 (s −1 ) under a temperature condition of 25 ° C. I went.
（スラリー組成物のスクリーン印刷性）
スクリーン印刷機（ミノグループ社製 商品名「ミノマットＹ−３５４０」）とＳＸスクリーン版（ミノグループ社製 商品名「ＳＸ３００Ｂ」）とを用いて、得られたスラリー組成物をセラミックグリーンシート上にスクリーン印刷し、印刷面を目視及び拡大顕微鏡で観察し、下記基準によりスクリーン印刷性を評価した。
(Screen printability of slurry composition)
Using a screen printing machine (trade name “Minomat Y-3540” manufactured by Mino Group) and an SX screen plate (trade name “SX300B” manufactured by Mino Group), the obtained slurry composition was screened on a ceramic green sheet. Printing was performed, and the printed surface was observed visually and with a magnifying microscope, and screen printability was evaluated according to the following criteria.
○ 印刷面に糸状のペーストやニジミが全く認められなかった。
△ 印刷面に糸状のペーストやニジミがわずかに認められた。
× 印刷面に糸状のペーストやニジミが多数認められた。
○ No thread-like paste or blemishes were found on the printed surface.
Δ: A slight amount of thread-like paste or blemishes was observed on the printed surface.
X A lot of thread-like paste and blemishes were observed on the printed surface.
本発明によれば、低粘度でハイソリッド化が可能であり、かつ、チキソトロピー性に優れ、印刷時の糸引き、目詰まり及びニジミを抑制することが可能な変性ポリビニルアセタール樹脂、並びに、該変性ポリビニルアセタール樹脂を用いてなるセラミックグリーンシート用スラリー組成物及びセラミックグリーンシートを提供できる。 According to the present invention, a modified polyvinyl acetal resin that can be made into a high solid with a low viscosity, has excellent thixotropy, and can suppress stringing, clogging, and blurring during printing, and the modification The slurry composition for ceramic green sheets and ceramic green sheet which use a polyvinyl acetal resin can be provided.
Claims (5)
アセタール単位内にスルホン酸基を有し、
前記α−オレフィン単位の含有量が２５〜５０モル％、前記スルホン酸基の含有量が０．１〜１０モル％、水酸基量が４０モル％以下である
ことを特徴とする変性ポリビニルアセタール樹脂。 A modified polyvinyl acetal resin having a sulfonic acid group in the molecule and an α-olefin unit in the main chain;
It has a sulfonic acid group in the acetal unit,
A modified polyvinyl acetal resin having a content of the α-olefin unit of 25 to 50 mol%, a content of the sulfonic acid group of 0.1 to 10 mol%, and a hydroxyl group content of 40 mol% or less.
A ceramic green sheet comprising the slurry composition for a ceramic green sheet according to claim 4.
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| WO2019159756A1 (en) * | 2018-02-14 | 2019-08-22 | 株式会社クラレ | Resin material, production method therefor, and water-soluble film |
| CN112585214A (en) * | 2018-09-26 | 2021-03-30 | 积水化学工业株式会社 | Epoxy resin composition |
| CN113646282A (en) * | 2019-03-28 | 2021-11-12 | 株式会社可乐丽 | Modified vinyl acetal resin for interlayer film of laminated glass |
| CN114981318A (en) * | 2020-01-15 | 2022-08-30 | 株式会社可乐丽 | Resin composition, resin sheet, and laminated glass |
| EP4163265A1 (en) * | 2021-10-11 | 2023-04-12 | Kuraray Europe GmbH | Use of ethylene vinyl acetals as binder in ceramic green sheets |
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| WO2019159757A1 (en) * | 2018-02-14 | 2019-08-22 | 株式会社クラレ | Modified vinyl alcohol polymer and production method therefor |
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| US20230069427A1 (en) * | 2020-01-15 | 2023-03-02 | Kuraray Co., Ltd. | Resin composition, resin sheet, and laminated glass |
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| WO2023061741A1 (en) * | 2021-10-11 | 2023-04-20 | Kuraray Europe Gmbh | Use of ethylene vinyl acetals as binder in ceramic green sheets |
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