EP4396151A1 - Use of ethylene vinyl acetals as binder in ceramic green sheets - Google Patents
Use of ethylene vinyl acetals as binder in ceramic green sheetsInfo
- Publication number
- EP4396151A1 EP4396151A1 EP22797316.1A EP22797316A EP4396151A1 EP 4396151 A1 EP4396151 A1 EP 4396151A1 EP 22797316 A EP22797316 A EP 22797316A EP 4396151 A1 EP4396151 A1 EP 4396151A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ethylene vinyl
- acetal
- mol
- ethylene
- binder
- 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.)
- Pending
Links
- 239000005977 Ethylene Substances 0.000 title claims abstract description 51
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 37
- -1 ethylene vinyl acetals Chemical class 0.000 title claims abstract description 31
- 239000000919 ceramic Substances 0.000 title claims abstract description 26
- 239000011230 binding agent Substances 0.000 title claims abstract description 24
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 239000004014 plasticizer Substances 0.000 claims abstract description 8
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 19
- 125000004036 acetal group Chemical group 0.000 claims description 8
- AMIMRNSIRUDHCM-UHFFFAOYSA-N isobutyric aldehyde Natural products CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 8
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- WDLUEZJSSHTKAP-UHFFFAOYSA-N acetaldehyde;1,1-diethoxyethane Chemical group CC=O.CCOC(C)OCC WDLUEZJSSHTKAP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000976 ink Substances 0.000 abstract 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 13
- 238000006359 acetalization reaction Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000001299 aldehydes Chemical class 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 239000011354 acetal resin Substances 0.000 description 5
- 150000001241 acetals Chemical class 0.000 description 5
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 5
- 229920006324 polyoxymethylene Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229940044613 1-propanol Drugs 0.000 description 2
- BOHKXQAJUVXBDQ-UHFFFAOYSA-N 2,3-dimethylpentanal Chemical compound CCC(C)C(C)C=O BOHKXQAJUVXBDQ-UHFFFAOYSA-N 0.000 description 2
- JGEGJYXHCFUMJF-UHFFFAOYSA-N 4-methylpentanal Chemical compound CC(C)CCC=O JGEGJYXHCFUMJF-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 235000019256 formaldehyde Nutrition 0.000 description 2
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BHVGMUDWABJNRC-UHFFFAOYSA-N (±)-2-methylhexanal Chemical compound CCCCC(C)C=O BHVGMUDWABJNRC-UHFFFAOYSA-N 0.000 description 1
- QYPLKDUOPJZROX-UHFFFAOYSA-N 2,2-dimethylbutanal Chemical compound CCC(C)(C)C=O QYPLKDUOPJZROX-UHFFFAOYSA-N 0.000 description 1
- YMXAGOUPXPGFLB-UHFFFAOYSA-N 2,2-dimethylpentanal Chemical compound CCCC(C)(C)C=O YMXAGOUPXPGFLB-UHFFFAOYSA-N 0.000 description 1
- FJJYHTVHBVXEEQ-UHFFFAOYSA-N 2,2-dimethylpropanal Chemical compound CC(C)(C)C=O FJJYHTVHBVXEEQ-UHFFFAOYSA-N 0.000 description 1
- AKUUEDVRXOZTBF-UHFFFAOYSA-N 2,3-dimethylbutanal Chemical compound CC(C)C(C)C=O AKUUEDVRXOZTBF-UHFFFAOYSA-N 0.000 description 1
- GPTMCJMLSOIYGU-UHFFFAOYSA-N 2,4-dimethylpentanal Chemical compound CC(C)CC(C)C=O GPTMCJMLSOIYGU-UHFFFAOYSA-N 0.000 description 1
- UNNGUFMVYQJGTD-UHFFFAOYSA-N 2-Ethylbutanal Chemical compound CCC(CC)C=O UNNGUFMVYQJGTD-UHFFFAOYSA-N 0.000 description 1
- FTZILAQGHINQQR-UHFFFAOYSA-N 2-Methylpentanal Chemical compound CCCC(C)C=O FTZILAQGHINQQR-UHFFFAOYSA-N 0.000 description 1
- BFKSYXOOFDWKFF-UHFFFAOYSA-N 2-ethyl-2-methylbutanal Chemical compound CCC(C)(CC)C=O BFKSYXOOFDWKFF-UHFFFAOYSA-N 0.000 description 1
- SHGPBDQRELYPLO-UHFFFAOYSA-N 2-ethyl-3-methylbutanal Chemical compound CCC(C=O)C(C)C SHGPBDQRELYPLO-UHFFFAOYSA-N 0.000 description 1
- OZGRFPZYTKHWMZ-UHFFFAOYSA-N 2-ethylpentanal Chemical compound CCCC(CC)C=O OZGRFPZYTKHWMZ-UHFFFAOYSA-N 0.000 description 1
- AXIZYEUPVXWMSV-UHFFFAOYSA-N 2-methylbutanal pentan-2-one Chemical compound CC(C=O)CC.C(C)(CCC)=O AXIZYEUPVXWMSV-UHFFFAOYSA-N 0.000 description 1
- LTNUSYNQZJZUSY-UHFFFAOYSA-N 3,3-dimethylbutanal Chemical compound CC(C)(C)CC=O LTNUSYNQZJZUSY-UHFFFAOYSA-N 0.000 description 1
- HPKCSWORDUPIJS-UHFFFAOYSA-N 3,3-dimethylpentanal Chemical compound CCC(C)(C)CC=O HPKCSWORDUPIJS-UHFFFAOYSA-N 0.000 description 1
- SZBNDYYJXRXQHA-UHFFFAOYSA-N 3,4-dimethylpentanal Chemical compound CC(C)C(C)CC=O SZBNDYYJXRXQHA-UHFFFAOYSA-N 0.000 description 1
- ZSJUABCTGCNBPF-UHFFFAOYSA-N 3-Methylhexanal Chemical compound CCCC(C)CC=O ZSJUABCTGCNBPF-UHFFFAOYSA-N 0.000 description 1
- XKJUKVTZSPIGSI-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O.CC(C)CC=O XKJUKVTZSPIGSI-UHFFFAOYSA-N 0.000 description 1
- YJWJGLQYQJGEEP-UHFFFAOYSA-N 3-methylpentanal Chemical compound CCC(C)CC=O YJWJGLQYQJGEEP-UHFFFAOYSA-N 0.000 description 1
- DZWACSVTJIDBDB-UHFFFAOYSA-N 4,4-dimethylpentanal Chemical compound CC(C)(C)CCC=O DZWACSVTJIDBDB-UHFFFAOYSA-N 0.000 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- GIGNTOMJQYNUNL-UHFFFAOYSA-N 4-methylhexanal Chemical compound CCC(C)CCC=O GIGNTOMJQYNUNL-UHFFFAOYSA-N 0.000 description 1
- GEKRISJWBAIIAA-UHFFFAOYSA-N 5-methylhexanal Chemical compound CC(C)CCCC=O GEKRISJWBAIIAA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003973 paint Substances 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
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
- 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
-
- 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
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
-
- 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
- C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63488—Polyethers, e.g. alkylphenol polyglycolether, polyethylene glycol [PEG], polyethylene oxide [PEO]
-
- 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
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6025—Tape casting, e.g. with a doctor blade
-
- 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
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/61—Mechanical properties, e.g. fracture toughness, hardness, Young's modulus or strength
-
- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9646—Optical properties
- C04B2235/9661—Colour
Definitions
- the invention is directed to the use of ethylene vinyl acetals as binder in ceramic green sheets.
- Ceramic materials like ceramic capacitors for the electronics industry are generally produced by sintering of a so-called green sheet, i.e. a film-like, thin moulded body, which contains the ceramic materials.
- a suspension of metal oxides, plasticizers, dispersing agents and binders in organic solvents is produced. This suspension is subsequently applied by means of a suitable process (i.e. doctor blade process) in the desired thickness onto a carrier film and the solvent is removed.
- a suitable process i.e. doctor blade process
- Polyvinyl acetals such as polyvinyl butyral are frequently used as binders for the production of ceramic green sheets.
- DE 4 003 198 A1 describes the production of a casting slip for ceramic green films in which polyvinyl butyral with a residual polyvinyl acetate content of 0 to 2% by weight is used as binder.
- MLCC multi-layer ceramic capacitors
- the size of the powder particles can be as small as 10 nm.
- the production demands an increased accuracy of the ceramic sheets used therein.
- the multi-layer stacks of ceramic green sheets are often wound up to a roll in the production process.
- the individual green sheets must possess superior properties with respect to binding and elongation-at-break. To this end, there is a need in the industry for further improved binders to be used in the suspensions.
- one objective of the invention was to provide binders for ceramic green sheets leading improved adhesion, improved elongation-at-break, improved dispersion effect, an improved environmental and safety impact and/or with a better economical profile in the production and use of the ceramic green sheet.
- the present invention concerns the use of an ethylene vinyl acetal as a binder for the production of a ceramic green sheet or a ceramic moulded body wherein the ethylene vinyl acetal comprises ethylene units in the range of 25 to 60 mol%.
- the ethylene vinyl acetal of the present invention can be obtained by subjecting an aldehyde to an acetalization reaction with an ethylene vinyl alcohol (EVOH).
- EVOH ethylene vinyl alcohol
- Such ethylene vinyl alcohols are known in the art and can be obtained by copolymerizing ethylene in the presence of an acidic catalyst. Furthermore, ethylene vinyl alcohols are commercially available.
- the ethylene vinyl alcohol is obtained by copolymerizing ethylene and a vinyl acetate and hydrolysing the obtained copolymer.
- a conventionally known alkali catalyst or an acid catalyst can be used and among them, a hydrolysation reaction using methanol as a solvent and caustic soda (NaOH) catalyst is convenient.
- the percentage of ethylene units in the ethylene vinyl alcohol is 25 to 60 mol%, more preferably 30 to 55 mol%, and still more preferably 35 to 50 mol%.
- the reaction product obtained after the acetalization reaction is neutralized with alkali, and then washed with water to obtain the ethylene vinyl acetal.
- the catalyst for carrying out the acetalization reaction is not particularly limited, and any organic acid or inorganic acid may be used. Examples thereof include acetic acid, para toluenesulfonic acid, nitric acid, sulfuric acid, hydrochloric acid, carbonic acid, and the like.
- the degree of saponification of the acetate groups is preferably 95 mol% or more, more preferably 98 mol% or more, still more preferably 99 mol% or more, and most preferably 99.9 mol% or more.
- the percentage of ethylene units in the ethylene vinyl acetal is 30 to 55 mol%, and more preferably 35 to 50 mol%. Also preferably, the percentage of ethylene units in the ethylene vinyl acetal is from 50 to 60 mol%.
- the acetal groups individually have 1 to 7 carbon atoms, i.e. they derive from the condensation reaction with aldehydes with 1 to 7 carbon atoms. More preferably, they derive from the list consisting of methanal (formaldehyde), acetaldehyde, n-propanal (propionaldehyde), n-butanal (butyraldehyde), iso-butanal (2-methyl-1 -propanal, iso-butyraldehyde), n-pentanal (valeraldeyhde), iso-pentanal (3-methyl-1 -butanal), sec-pentanal (2-methyl-1 -butanal), tert-pentanal (2,2,dimethyl- 1 -propanal), n-hexanal (capronaldehyde), iso-hexanal (2-methyl-1 -pentanal, 3- methyl-1 -pentanal, 4-methyl-1 -
- the method for producing the ethylene vinyl acetals used in this embodiment of the present invention can be produced by a method in which an aldehyde is added to an ethylene vinyl alcohol solution under acidic conditions and subjected to an acetalization reaction.
- the degree of acetalization of the ethylene vinyl acetal used in the present invention is 5 mol% or more and less than 40 mol%, more preferably the lower limit of the degree of acetalization is more than 6 mol%, more than 7 mol%, more than 8 mol%, more than 9 mol%, and most preferably more than 10 mol%.
- the upper limit of the degree of acetalization is more preferably 38 mol% or less, 36 mol% or less, 34 mol% or less, and 32 mol% or less in this order, and most preferably less than 30 mol%.
- the ethylene content of the ethylene vinyl acetate copolymer is measured by NMR spectroscopy.
- the ethylene vinyl acetal resin is dissolved in ethanol and a 2 N hydrochloride hydroxylamine solution and hydrochloric acid are added, and the mixture is stirred under reflux with a condenser in a water bath for 4 hours, and after cooling, ammonia water is added.
- methanol is added and the polymer is precipitated, washed and dried to obtain the acetylated ethylene vinyl alcohol copolymer.
- the present invention concerns a suspension composition
- a suspension composition comprising one or more inorganic pigments, one or more organic solvents, one or more binders, one or more plasticizers, and one or more dispersing agents, wherein the binder is an ethylene vinyl acetal comprising ethylene units in the range of 25 to 60 mol%.
- the inorganic pigments can be chosen from finely ground granules of paraelectric or ferroelectric raw materials and include titanium dioxide (rutile), preferably modified by additives of zinc, zirconium, niobium, magnesium, tantalum, cobalt and/or strontium, as well as compounds chosen from MgNb2Oe, ZnNb2Oe, MgTa2Oe, ZnTa2Oe, (ZnMg)TiOs, (ZrSn)TiC>4 and Ba2Tig02o or BaTiC (Barium titanate).
- the average particle diameter of the inorganic pigments is preferably about 0.01 to 1 pm.
- Suitable dispersing agents include fish oil, phosphoric acid esters and functional polymers comprising polyoxyalkylene groups on side chain, such as the MALIALIMTM series commercially available from NOF America Cooperation.
- a method of using a media- type mill such as a bead mill, a ball mill, an attritor, a paint shaker and a sand mill; a method of kneading a powdered ceramic, a dispersing medium, a dispersing agent, a binder, a plasticizer and the like; and a method of using a three-roll mill.
- a three-roll mill the method includes dispersing a powdered inorganic pigment in an organic solvent (mixture) together with a dispersing agent, a binder, a plasticizer, and the like.
- the powdered ceramic, dispersing agent, and solvent (mixture) are premixed and dispersed so that the dispersing agent is adsorbed on the powdered ceramic.
- the binder is added to the mixture thus formed, and subsequently, mixing and dispersing is performed again.
- the PVB solution is used a binder solution to prepare a ceramic green sheet. Details on the description for the green sheet preparation is in the following section.
- a resin solution was prepared by adding 10.4 g of the (polyvinyl) acetal resin and 3.95 g of the plasticizer 3G8 to a mixed solvent of 59.8 g of ethanol and 59.8 g of toluene. Mixture is stirred to dissolve the resin.
- the ZrO2-beads were separated from the dispersion using a nylon screen/filter.
- the obtained dispersion was degassed and casted according to the doctor blade process using an automized film application machine.
- a siliconized PET (Hostaphan® RN 2 SLK, thickness 75 pm) was used as casting support. After casting, the film was dried in the air for 24 h (temperature: 23 °C, relative humidity: 50%) and subsequently drawn off.
- the films obtained had a thickness of 15 pm and exhibited to cracks, blisters or defects during optical assessment.
- the results of the tensile test show that the ceramic green sheets obtained with the ethylene vinyl acetal have a value for the elongation at break of more than double of that obtained with the PVB standard.
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- Chemical & Material Sciences (AREA)
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Abstract
The invention is directed to the use of certain ethylene vinyl acetals as binders in printing inks. A suspension composition comprising one or more inorganic pigments, one or more organic solvents, one or more binders, one or more plasticizers, and one or more dispersing agents, wherein the binder is an ethylene vinyl acetal comprising ethylene units in the range of 25 to 60 mol% is disclosed. A process for the production of a ceramic green sheet or a ceramic moulded body using the suspension is also disclosed.
Description
Use of ethylene vinyl acetals as binder in ceramic green sheets
The invention is directed to the use of ethylene vinyl acetals as binder in ceramic green sheets.
Ceramic materials like ceramic capacitors for the electronics industry are generally produced by sintering of a so-called green sheet, i.e. a film-like, thin moulded body, which contains the ceramic materials. For the production of these green sheets, a suspension of metal oxides, plasticizers, dispersing agents and binders in organic solvents is produced. This suspension is subsequently applied by means of a suitable process (i.e. doctor blade process) in the desired thickness onto a carrier film and the solvent is removed. The green sheet thus obtained must be free from cracks, exhibit a smooth surface and still have a certain elasticity.
Polyvinyl acetals such as polyvinyl butyral are frequently used as binders for the production of ceramic green sheets. To this end, DE 4 003 198 A1 describes the production of a casting slip for ceramic green films in which polyvinyl butyral with a residual polyvinyl acetate content of 0 to 2% by weight is used as binder.
In recent years, multi-layer ceramic capacitors (MLCC) are becoming increasingly important for the electronics industry. MLCCs consist of a number of individual capacitors stacked together in parallel and contacted via the terminal surfaces. Due to the advancing miniaturization of the electronic components, the size of the powder particles can be as small as 10 nm. Hence, the production demands an increased accuracy of the ceramic sheets used therein. Additionally, the multi-layer stacks of ceramic green sheets are often wound up to a roll in the production process. To avoid delamination, the individual green sheets must possess superior properties with respect to binding and elongation-at-break. To this end, there is a need in the industry for further improved binders to be used in the suspensions.
Accordingly, one objective of the invention was to provide binders for ceramic green sheets leading improved adhesion, improved elongation-at-break, improved dispersion effect, an improved environmental and safety impact and/or with a better economical profile in the production and use of the ceramic green sheet.
It has been found that these and other certain ethylene vinyl acetals are highly suitable as binders for the production of ceramic suspensions and consequently for the production of ceramic green sheets.
Accordingly, the present invention concerns the use of an ethylene vinyl acetal as a binder for the production of a ceramic green sheet or a ceramic moulded body wherein the ethylene vinyl acetal comprises ethylene units in the range of 25 to 60 mol%.
The ethylene vinyl acetal of the present invention can be obtained by subjecting an aldehyde to an acetalization reaction with an ethylene vinyl alcohol (EVOH). Such ethylene vinyl alcohols are known in the art and can be obtained by copolymerizing ethylene in the presence of an acidic catalyst. Furthermore, ethylene vinyl alcohols are commercially available.
Preferably, the ethylene vinyl alcohol is obtained by copolymerizing ethylene and a vinyl acetate and hydrolysing the obtained copolymer. In the hydrolysation reaction, a conventionally known alkali catalyst or an acid catalyst can be used and among them, a hydrolysation reaction using methanol as a solvent and caustic soda (NaOH) catalyst is convenient.
Preferably, the percentage of ethylene units in the ethylene vinyl alcohol is 25 to 60 mol%, more preferably 30 to 55 mol%, and still more preferably 35 to 50 mol%.
The reaction product obtained after the acetalization reaction is neutralized with alkali, and then washed with water to obtain the ethylene vinyl acetal.
The catalyst for carrying out the acetalization reaction is not particularly limited, and any organic acid or inorganic acid may be used. Examples thereof include acetic acid, para toluenesulfonic acid, nitric acid, sulfuric acid, hydrochloric acid, carbonic acid, and the like.
Although there is no particular limitation on the degree of saponification of the acetate groups, it is preferably 95 mol% or more, more preferably 98 mol% or more, still more preferably 99 mol% or more, and most preferably 99.9 mol% or more.
Preferably, the percentage of ethylene units in the ethylene vinyl acetal is 30 to 55 mol%, and more preferably 35 to 50 mol%. Also preferably, the percentage of ethylene units in the ethylene vinyl acetal is from 50 to 60 mol%.
Preferably, the acetal groups individually have 1 to 7 carbon atoms, i.e. they derive from the condensation reaction with aldehydes with 1 to 7 carbon atoms. More preferably, they derive from the list consisting of methanal (formaldehyde), acetaldehyde, n-propanal (propionaldehyde), n-butanal (butyraldehyde), iso-butanal (2-methyl-1 -propanal, iso-butyraldehyde), n-pentanal (valeraldeyhde), iso-pentanal (3-methyl-1 -butanal), sec-pentanal (2-methyl-1 -butanal), tert-pentanal (2,2,dimethyl- 1 -propanal), n-hexanal (capronaldehyde), iso-hexanal (2-methyl-1 -pentanal, 3- methyl-1 -pentanal, 4-methyl-1 -pentanal), 2, 2-dimethyl-1 -butanal, 2,3-dimethyl-1 - butanal, 3, 3-dimethyl-1 -butanal, 2-ethyl-1 -butanal, n-heptanal, 2-methyl-1 -hexanal, 3- methyl-1 -hexanal, 4-methyl-1 -hexanal, 5-methyl-1 -hexanal, 2,2-dimethyl-1 -pentanal, 3,3-dimethyl-1 -pentanal, 4,4-dimethyl-1 -pentanal, 2,3-dimethyl-1 -pentanal, 2,4- dimethyl-1 -pentanal, 3, 4-dimethyl-1 -pentanal, 2-ethyl-1 -pentanal, 2-ethyl-2-methyl-1 - butanal, 2-ethyl-3-methyl-1 -butanal, 3-ethyl-2-methyl-1 -butanal, cyclohexylaldehyde and benzaldehyde. Most preferably, they derive from the condensation reaction with iso-butyraldehyde, acetaldehyde and/or n-butyraldehyde.
Also preferably, the ethylene vinyl acetals according to the present invention are mixed acetals, i.e. they comprise at least two different acetal groups. In other words, the ethylene vinyl acetals as used in the invention comprise a first acetal group derived from the reaction of two hydroxyl groups of the respective ethylene vinyl alcohol with one aldehyde and at least a second acetal group derived from the reaction of two other hydroxyl groups of the respective ethylene vinyl alcohol with a second aldehyde, wherein the first aldehyde is different from the second aldehyde. The preferred aldehydes are the same as used for the acetals with one acetal group as listed above; the most preferable combination is a mixture of acetals derived from acetaldehyde and n-butyraldehyde.
Although there is no particular limitation to the method for producing the ethylene vinyl acetals used in this embodiment of the present invention, they can be produced by a method in which an aldehyde is added to an ethylene vinyl alcohol solution under acidic conditions and subjected to an acetalization reaction.
Preferably, the degree of acetalization of the ethylene vinyl acetal used in the present invention is 5 mol% or more and less than 40 mol%, more preferably the lower limit of the degree of acetalization is more than 6 mol%, more than 7 mol%, more than 8 mol%, more than 9 mol%, and most preferably more than 10 mol%. Further, the upper limit of the degree of acetalization is more preferably 38 mol% or less, 36 mol% or less, 34 mol% or less, and 32 mol% or less in this order, and most preferably less than 30 mol%.
Preferably, the percentage of vinyl alcohol units in the ethylene vinyl acetal resin of the present invention is 24 to 71 mol% based on the total monomer unit constituting the resin.
The vinyl alcohol content and vinyl acetate content of ethylene vinyl acetals were determined in accordance with DIN ISO 3681 (acetate content) and DIN ISO 53240
(PVA content). The vinyl acetal content is calculated as the remaining portion from the sum of vinyl alcohol content and vinyl acetate content determined in accordance with DIN ISO 53401/53240 and the ethylene needed to make one hundred. The degree of acetalization is calculated from the amount of vinyl acetal content divided by the sum of vinyl alcohol content, vinyl acetal content and vinyl acetate content. Conversion from % by weight into mol % is achieved by formulas known to the person skilled in the art.
The ethylene content of the ethylene vinyl acetate copolymer is measured by NMR spectroscopy. First, the ethylene vinyl acetal resin is dissolved in ethanol and a 2 N hydrochloride hydroxylamine solution and hydrochloric acid are added, and the mixture is stirred under reflux with a condenser in a water bath for 4 hours, and after cooling, ammonia water is added. Afterwards, methanol is added and the polymer is precipitated, washed and dried to obtain the acetylated ethylene vinyl alcohol copolymer. Then, the acetylated ethylene vinyl alcohol copolymer is dissolved in DMSO (dimethyl sulfoxide) at 120 °C, cooled to room temperature, and then N,N- dimethyl-4-aminopyridine and acetic anhydride are added thereto, followed by stirring for 1 h, followed by precipitation with ion-exchanged water and acetone, and drying to obtain an ethylene vinyl acetate copolymer. The polymer is dissolved in DMSO-d6 and measured by a proton NMR spectrometer of 400 MHz The spectrum obtained was integrated 256 times. The molar ratio of the ethylene units of the ethylene vinyl alcohol copolymer is calculated from the intensity ratio of the methine proton (peak of 1.1 to 1 .9 ppm) derived from the ethylene unit and the vinyl acetate unit, and the terminal methyl proton (peak of 2.0ppm) derived from the vinyl acetate unit. Note that, since the ethylene unit is not affected by the acetalization reaction, the molar ratio (n) of the ethylene unit of the ethylene vinyl alcohol copolymer before the acetalization reaction is equal to the molar ratio (n) of the ethylene unit of the ethylene vinyl acetal resin obtained after the acetalization reaction.
In a second aspect, the present invention concerns a suspension composition comprising one or more inorganic pigments, one or more organic solvents, one or more binders, one or more plasticizers, and one or more dispersing agents, wherein
the binder is an ethylene vinyl acetal comprising ethylene units in the range of 25 to 60 mol%.
Preferably, the acetal group has 2 to 7 carbon atoms and is derived from the same aldehyde(s) as described above. Most preferably, the ethylene vinyl acetal comprises n-butyraldehyde and/or acetaldehyde acetal groups.
The inorganic pigments can be chosen from finely ground granules of paraelectric or ferroelectric raw materials and include titanium dioxide (rutile), preferably modified by additives of zinc, zirconium, niobium, magnesium, tantalum, cobalt and/or strontium, as well as compounds chosen from MgNb2Oe, ZnNb2Oe, MgTa2Oe, ZnTa2Oe, (ZnMg)TiOs, (ZrSn)TiC>4 and Ba2Tig02o or BaTiC (Barium titanate). The average particle diameter of the inorganic pigments is preferably about 0.01 to 1 pm.
The organic solvent may be chosen from aromatic compounds, such as toluene and xylene, and alcohol compounds, such as ethyl alcohol, isopropyl alcohol and butyl alcohol and more preferably, mixtures thereof.
Suitable dispersing agents include fish oil, phosphoric acid esters and functional polymers comprising polyoxyalkylene groups on side chain, such as the MALIALIM™ series commercially available from NOF America Cooperation.
In addition to the binder according to the present invention, the suspension may comprise other components chosen inter alia from other binders like cellulose resins, acrylic resins, vinyl acetate resins, polyvinyl alcohol resins; plasticizers such as polyethylene glycol or phthalic esters, and/or a defoamer.
The method to produce the suspension composition is not specifically limited.
Various dispersing methods may be used, for example, a method of using a media-
type mill, such as a bead mill, a ball mill, an attritor, a paint shaker and a sand mill; a method of kneading a powdered ceramic, a dispersing medium, a dispersing agent, a binder, a plasticizer and the like; and a method of using a three-roll mill. Using a three-roll mill, the method includes dispersing a powdered inorganic pigment in an organic solvent (mixture) together with a dispersing agent, a binder, a plasticizer, and the like.
Preferably, the powdered ceramic, dispersing agent, and solvent (mixture) are premixed and dispersed so that the dispersing agent is adsorbed on the powdered ceramic. In a second step, the binder is added to the mixture thus formed, and subsequently, mixing and dispersing is performed again.
The thickness of the coating film produced by these processes can be 0.25 to 25 pm, and typically, 0.5 to 10 pm.
Examples
Example 1 - ethylene vinyl acetal
100 parts by weight of the ethylene vinyl alcohol copolymer synthesized according to the process described in Japanese Patent Application Laid-Open No. 2016-28139 were dispersed in 315 parts by weight of 1 -propanol containing 44 mol% of ethylene units (saponification degree: 99%) and the temperature of the solution was raised to 60 °C with agitation. Afterwards, 40 parts by weight of 1 M hydrochloric acid was added, followed by 34.2 parts by weight of n-butyraldehyde while maintaining the temperature at 60 °C. As the reaction proceeded, the ethylene vinyl alcohol copolymer dissolved and the reaction mixture became a homogeneous solution. After 36 hours, 6.4 parts by weight of sodium hydrogen carbonate was added to stop the reaction. After adding 500 parts by weight of 1 -propanol to the reaction solution to make it uniform, it was added dropwise to 2000 parts by weight of water to precipitate a resin. Thereafter, the operation of filtration and washing with water was repeated three times, the resulting solid was vacuum dried at 60 °C for 8 hours. The ethylene
vinyl acetal thus obtained has a content of ethylene units of 44 mol% and an degree of acetalization of 46 mol%.
1 - n-butyl acetal
Mowital® polyvinyl acetal resin B 75 H obtained from Kuraray Europe GmbH, which contains acetal units prepared from n-butyraldehyde and a polyvinyl alcohol with no ethylene units in the polymer chain, is used to prepare a PVB solution. The PVB solution is used a binder solution to prepare a ceramic green sheet. Details on the description for the green sheet preparation is in the following section.
Preparation of inorganic dispersion
1 .3 g of a polyoxyalkylene dispersing agent (MALI ALIM™ series, name: SC-0505K, supplier: NOF) was added to a mixed solvent of 25 g of toluene and 25 g of ethanol and dissolved by stirring. Next, 130 g of barium titanate powder (manufactured by Fuji Titanium Industry, UQBT-20) and 500 g of ZrC>2 beads (diameter: 2 mm) were added to the obtained solution. The organic dispersion was mixed for 6-8 hours on a roller mixer.
Preparation of resin solution
A resin solution was prepared by adding 10.4 g of the (polyvinyl) acetal resin and 3.95 g of the plasticizer 3G8 to a mixed solvent of 59.8 g of ethanol and 59.8 g of toluene. Mixture is stirred to dissolve the resin.
Ceramic green sheet production
The resin solution was added to the obtained inorganic dispersion and mixed using a roller block mixer for 10 h to obtain a composition for a ceramic green sheet.
The ZrO2-beads were separated from the dispersion using a nylon screen/filter.
The obtained dispersion was degassed and casted according to the doctor blade process using an automized film application machine. A siliconized PET (Hostaphan® RN 2 SLK, thickness 75 pm) was used as casting support. After casting, the film was
dried in the air for 24 h (temperature: 23 °C, relative humidity: 50%) and subsequently drawn off.
The films obtained had a thickness of 15 pm and exhibited to cracks, blisters or defects during optical assessment.
From the green sheets concerned, suitable tensile specimens in the form of a so-called “dog bones” were punched out. 8 tensile specimens per type of film were punched out cross to the direction of casting and inspected by human eye. The 4 specimen which appeared to have the least flaws from the punching process were selected for measurement for both example 1 and comparable example 1 . A universal tensile test machine was used for tensile force measurement. The measurements were carried under controlled conditions, being 23 °C and 50% relative humidity in accordance with DIN EN ISO 527-1 and DIN EN ISO 527-3.
Table 1 : Results of the tensile test
The results of the tensile test show that the ceramic green sheets obtained with the ethylene vinyl acetal have a value for the elongation at break of more than double of that obtained with the PVB standard.
Claims
1 . Use of an ethylene vinyl acetal as a binder for the production of a ceramic green sheet or a ceramic moulded body wherein the ethylene vinyl acetal comprises ethylene units in the range of 25 to 60 mol%.
2. The use according to claim 1 wherein the acetal group has 2 to 7 carbon atoms.
3. The use according to claim 1 or 2 wherein the ethylene vinyl acetal comprises n-butyraldehyde and/or iso-butyraldehyde acetal groups.
4. The use according to any one of claims 1 to 3 wherein the residual vinyl alcohol in the ethylene vinyl acetals is 15 to 40 mol%.
5. A suspension composition comprising one or more inorganic pigments, one or more organic solvents, one or more binders, one or more plasticizers, and one or more dispersing agents, wherein the binder is an ethylene vinyl acetal comprising ethylene units in the range of 25 to 60 mol%.
6. The suspension according to claim 5 wherein the acetal group has 2 to 7 carbon atoms.
7. The suspension according to claim 5 or 6 wherein the ethylene vinyl acetal comprises n-butyraldehyde and/or acetaldehyde acetal groups.
8. A process for the production of a ceramic green sheet or a ceramic moulded body using the suspension according to any one of claims 5 to 7.
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EP21201836.0A EP4163265A1 (en) | 2021-10-11 | 2021-10-11 | Use of ethylene vinyl acetals as binder in ceramic green sheets |
PCT/EP2022/076702 WO2023061741A1 (en) | 2021-10-11 | 2022-09-26 | Use of ethylene vinyl acetals as binder in ceramic green sheets |
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EP21201836.0A Withdrawn EP4163265A1 (en) | 2021-10-11 | 2021-10-11 | Use of ethylene vinyl acetals as binder in ceramic green sheets |
EP22797316.1A Pending EP4396151A1 (en) | 2021-10-11 | 2022-09-26 | Use of ethylene vinyl acetals as binder in ceramic green sheets |
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DE4003198A1 (en) | 1990-02-03 | 1991-08-08 | Hoechst Ceram Tec Ag | Casting compsns. for prepn. of ceramic green films - contain ceramic powder, organic solvent, plasticiser, dispersant, and polyvinyl butyral contg. vinyl] alcohol and vinyl] acetate units |
JP6239841B2 (en) * | 2013-03-27 | 2017-11-29 | 積水化学工業株式会社 | Slurry composition for ceramic green sheet |
JP6178093B2 (en) * | 2013-03-29 | 2017-08-09 | 積水化学工業株式会社 | Modified polyvinyl acetal resin |
EP2963496B1 (en) * | 2014-06-30 | 2017-04-05 | Agfa Graphics NV | A lithographic printing plate precursor including ( ethylene, vinyl acetal ) copolymers |
JP6704688B2 (en) | 2014-07-11 | 2020-06-03 | 株式会社クラレ | Resin composition and multilayer structure |
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