CN105517698A - Polymer dispersant for inorganic pigment - Google Patents
Polymer dispersant for inorganic pigment Download PDFInfo
- Publication number
- CN105517698A CN105517698A CN201480049250.2A CN201480049250A CN105517698A CN 105517698 A CN105517698 A CN 105517698A CN 201480049250 A CN201480049250 A CN 201480049250A CN 105517698 A CN105517698 A CN 105517698A
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- construction unit
- inorganic pigments
- methyl
- quality
- formula
- Prior art date
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- 239000001023 inorganic pigment Substances 0.000 title claims abstract description 146
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 95
- 229920000642 polymer Polymers 0.000 title abstract description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 54
- 238000010276 construction Methods 0.000 claims description 131
- 150000001875 compounds Chemical class 0.000 claims description 44
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 41
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 40
- -1 stearyl acrylate ester Chemical class 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000049 pigment Substances 0.000 claims description 18
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 17
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 15
- 239000011707 mineral Substances 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 12
- 229910002113 barium titanate Inorganic materials 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 239000011354 acetal resin Substances 0.000 claims description 5
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 5
- 125000001118 alkylidene group Chemical group 0.000 claims description 5
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 5
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 5
- 229920006324 polyoxymethylene Polymers 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021523 barium zirconate Inorganic materials 0.000 claims description 4
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 claims description 4
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000470 constituent Substances 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 abstract description 2
- 239000003125 aqueous solvent Substances 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 22
- 239000002245 particle Substances 0.000 description 22
- 239000006185 dispersion Substances 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 19
- 239000007788 liquid Substances 0.000 description 14
- 239000002585 base Substances 0.000 description 12
- 229920001223 polyethylene glycol Polymers 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000000523 sample Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 10
- 229920002521 macromolecule Polymers 0.000 description 10
- 239000003292 glue Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 229920001427 mPEG Polymers 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000008676 import Effects 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002296 dynamic light scattering Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XMGZWGBXVLJOKE-UHFFFAOYSA-N acetic acid;toluene Chemical compound CC(O)=O.CC1=CC=CC=C1 XMGZWGBXVLJOKE-UHFFFAOYSA-N 0.000 description 2
- 238000002479 acid--base titration Methods 0.000 description 2
- 239000012445 acidic reagent Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- UMSCPKPEJAYDKK-UHFFFAOYSA-N butan-1-amine;toluene Chemical compound CCCCN.CC1=CC=CC=C1 UMSCPKPEJAYDKK-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- CVEPFOUZABPRMK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;styrene Chemical compound CC(=C)C(O)=O.C=CC1=CC=CC=C1 CVEPFOUZABPRMK-UHFFFAOYSA-N 0.000 description 1
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 1
- MBGYSHXGENGTBP-UHFFFAOYSA-N 6-(2-ethylhexoxy)-6-oxohexanoic acid Chemical compound CCCCC(CC)COC(=O)CCCCC(O)=O MBGYSHXGENGTBP-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- KZXBYXMHGCRRGF-UHFFFAOYSA-N N-(3-methoxypropyl)-N-methylprop-2-enamide Chemical compound COCCCN(C)C(=O)C=C KZXBYXMHGCRRGF-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical class NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- YCZJVRCZIPDYHH-UHFFFAOYSA-N ditridecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCCC YCZJVRCZIPDYHH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- OWVWGCVNBQLTDH-UHFFFAOYSA-N n-butyl-n-methylprop-2-enamide Chemical compound CCCCN(C)C(=O)C=C OWVWGCVNBQLTDH-UHFFFAOYSA-N 0.000 description 1
- CSGOAFRNKNQONI-UHFFFAOYSA-N n-dodecyl-n-methylprop-2-enamide Chemical compound CCCCCCCCCCCCN(C)C(=O)C=C CSGOAFRNKNQONI-UHFFFAOYSA-N 0.000 description 1
- SLBRDIJOHKHAAR-UHFFFAOYSA-N n-methyl-n-octadecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCCCN(C)C(=O)C=C SLBRDIJOHKHAAR-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012488 sample solution Substances 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
- 239000006228 supernatant Substances 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
- C09K23/44—Ether carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
- C09B67/0085—Non common dispersing agents
- C09B67/009—Non common dispersing agents polymeric dispersing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/006—Metal
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/007—Metal oxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/002—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Colloid Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Provided is a polymer dispersant for an inorganic pigment, with which it is possible to produce a ceramic sheet having excellent sheet detachability and inorganic pigment dispersability. One embodiment of the present invention relates to a polymer dispersant for an inorganic pigment used in a non-aqueous solvent, said polymer dispersant including a copolymer that contains, in total constituent units, 1 mass% to 45 mass% inclusive of a constituent unit (a) represented by formula (1), and 55 mass% to 99 mass% inclusive of a constituent unit (b) represented by formula (2).
Description
Technical field
The present invention is about a kind of high-molecular dispersant for inorganic pigments, the process for dispersing using it and paste compound.
Prior art
In the high technology ceramics field etc. using inorganic pigment, attempt by the fine structure controlling nanoscale and realize miniaturization, high speed, low power consumption, high efficiency, high capacity.
Patent document 1 discloses a kind of resin glue, and it is for the inorganic microparticle-dispersed paste composition containing inorganic particles.
Patent document 2 discloses a kind of high-molecular dispersant for inorganic pigments, and it contains 3 construction units of the construction unit comprising and have acidic group and the construction unit with huge monomer etc.
Prior art document
Patent document
Patent document 1: Japanese Patent Laid-Open 2009-144079 publication
Patent document 2:WO2010/024186 description
Summary of the invention
Invention institute for solution problem
Higher to the requirement of the nano-dispersed technology of the basic mineral pigment in non-water system, require that the performance of dispersant is improved further.For the potsherd representated by the raw cook that laminated ceramic capacitor uses, with the filming of sheet, also require the improvement of the treatability such as the fissility of the potsherd after coating sizing-agent (following, to be also called " sheet fissility ").Patent document 1 mentions that using containing oxirane repeat number is that the methacrylate copolymer of the polyglycol chain of 90 is as resin glue.But the document not about high-molecular dispersant for inorganic pigments, and about inorganic pigment resin glue, thus thinks that the dispersion of inorganic pigment is insufficient.On the other hand, a kind of macromolecule dispersing agent mentioned by patent document 2, and it is that the polyethylene glycol of 23 is as the dispersant making barium titanate particles high dispersive that this macromolecule dispersing agent contains average addition molal quantity.But sheet fissility has the leeway of improving further.
Therefore, the present invention provides a kind of high-molecular dispersant for inorganic pigments manufacturing the dispersiveness of inorganic pigment and the potsherd of sheet fissility excellence in a mode.
The technological means of dealing with problems
The present invention is (following about a kind of high-molecular dispersant for inorganic pigments in a mode, also be called " dispersant of the present invention "), this high-molecular dispersant for inorganic pigments to be included in general construction unit containing more than construction unit (a) 1 quality % represented by formula (1) and below 45 quality % and more than construction unit (b) the 55 quality % represented by formula (2) and the copolymer of below 99 quality % is (following, also be called " copolymer of the present invention "), and use in non-water solvent.
[changing 1]
[in formula (1), R
1, R
2and R
3identical or different, represent hydrogen atom, methyl or ethyl, M represents hydrogen atom or cation.]
[changing 2]
[in formula (2), R
4, R
5, R
6and R
8identical or different, represent hydrogen atom, methyl or ethyl, R
7represent that carbon number is more than 2 and the alkylidene of the straight or branched of less than 4, X
1represent that oxygen atom or NH, n are-R
7the average addition molal quantity of-O-base, represent more than 50 and be less than 140 number.]
The present invention is about a kind of process for dispersing in another mode, and this process for dispersing uses high-molecular dispersant for inorganic pigments of the present invention and basic mineral pigment is disperseed.
The present invention is about a kind of paste compound (following, to be also called " paste compound of the present invention ") in another mode, and this paste compound contains non-water solvent, basic mineral pigment and high-molecular dispersant for inorganic pigments of the present invention.
Invention effect
High-molecular dispersant for inorganic pigments of the present invention can play following effect in one or more embodiment: make inorganic pigment particles high dispersive in non-water solvent, and can reduce the peeling force when mold release film peels off the potsherd formed by the paste compound containing this dispersant.By this, in one or more embodiment, the present invention can play and make the process of potsherd become easier effect.
Detailed description of the invention
The present inventor finds: in the copolymer containing the construction unit (a) with acidic group represented by formula (1) and the construction unit (b) represented by formula (2), each construction unit is existed with specific ratio, the good dispersiveness of inorganic pigment can be realized by this in non-water solvent, and can improved sheet fissility.In this announcement, so-called " realizing the good dispersiveness of inorganic pigment ", refers in one or more embodiment, can make inorganic pigment be separated into primary particle size state or close to its state, even and if then add resin glue, also can maintain good dispersiveness.In this announcement, so-called " improved sheet fissility ", refers in one or more embodiment, reduces the peeling force when mold release film peels off the potsherd formed by the paste compound comprising inorganic pigment and macromolecule dispersing agent.
Though the details that can realize the mechanism of the good dispersiveness of the inorganic pigment in non-water solvent are still not clear, be inferred as follows.Think: first, the construction unit (a) by the copolymer in dispersant of the present invention is mainly adsorbed in inorganic pigment surface strongly, and suppresses this copolymer to depart from from inorganic pigment surface, thus copolymer can be coated to inorganic pigment surface.Further, because the construction unit (b) of this copolymer mainly brings stronger three-dimensional repulsion between inorganic pigment particles, therefore can alleviate inorganic pigment particles cohesion each other or the interaction with resin glue thereafter, improve so dispersed.
Though can the details of mechanism of improved sheet fissility be still not clear, be inferred as follows.That is, the oblong link oxyalkyl had by the construction unit (b) of this copolymer acts on the interface of the mold release film higher with hydrophobicity, thus the interaction of potsherd and mold release film weakens.By this, think that sheet fissility improves, the treatability of potsherd also improves.
But these are for inferring, the present invention is not limited to these mechanism.
Dispersant of the present invention comprises copolymer of the present invention in one or more embodiment.Dispersant of the present invention can comprise copolymer of the present invention and and then comprise other compositions in one or more embodiment.Other compositions can enumerate solvent, plasticizer, antistatic additive, resin glue etc. in one or more embodiments of not circumscribed.
[construction unit (a)]
The construction unit of construction unit (a) in copolymer of the present invention represented by formula (1).Construction unit (a), for having the acidic groups person that can neutralize, is thought and is had by being adsorbed in inorganic pigment surface strongly and suppress the effect that copolymer departs from from inorganic pigment surface.
[changing 3]
In formula (1), R
1, R
2and R
3identical or different, represent hydrogen atom, methyl or ethyl, M represents hydrogen atom or cation.
With regard to improve the dispersiveness of inorganic pigment and the viewpoint of improved sheet fissility and in copolymer the easiness of guiding structure unit (a) viewpoint with regard to, R
1and R
2be preferably hydrogen atom or methyl, be more preferably hydrogen atom, R
3be preferably hydrogen atom or methyl, be more preferably methyl.As the cation of M, in one or more embodiment, ammonium, organic ammonium etc. can be enumerated.With regard to regard to described identical viewpoint, M is preferably hydrogen atom.
As construction unit (a), can enumerate that to be derived from the monomer with carboxyl (following, also be called " monomer (a) ") construction unit or after polymerization, import carboxyl and the construction unit etc. that obtains, with regard to the viewpoint of the easiness of manufacture, be preferably derived from the construction unit of monomer (a).With regard to the viewpoint of easiness manufactured, construction unit (a) is preferably derived from can with the construction unit with the monomer of ethene unsaturated double-bond of monomer copolymerization forming construction unit (b).
As monomer (a), with regard to the raising dispersiveness of inorganic pigment and the viewpoint of improved sheet fissility, be preferably the monomer represented by formula (4).
[changing 4]
In formula (4), R
1, R
2and R
3identical or different, represent hydrogen atom, methyl or ethyl, M represents hydrogen atom or cation.
In formula (4), R
1, R
2, R
3and M is identical with said structure unit (a) in one or more embodiment.
As monomer (a), (methyl) acrylic acid, crotonic acid etc. can be enumerated, with regard to improve inorganic pigment dispersiveness and in copolymer the easiness of guiding structure unit (a) viewpoint with regard to, be preferably (methyl) acrylic acid, be more preferably methacrylic acid.In this description, so-called " (methyl) acrylic acid ", means to be selected from least one in acrylic acid and methacrylic acid.
About the ratio of the construction unit (a) formed in the general construction unit of copolymer of the present invention, with regard to improve the adsorption rate of inorganic pigment is improved to the dispersiveness of inorganic pigment aspect for, be more than 1 quality %, be preferably more than 3 quality %, be more preferably more than 5 quality %, and then be preferably more than 8 quality %, and then be preferably more than 12 quality %, with regard to identical viewpoint, be below 45 quality %, be preferably below 35 quality %, be more preferably below 24 quality %, and then be preferably below 18 quality %.
[construction unit (b)]
The construction unit of construction unit (b) in copolymer of the present invention represented by formula (2).Construction unit (b) is nonionic, think and show following effect: between inorganic pigment particles, bring stronger three-dimensional repulsion, and suppress inorganic pigment particles cohesion each other, and reduce the interaction of potsherd and mold release film, thus improve fissility.
[changing 5]
In formula (2), R
4, R
5, R
6and R
8identical or different, represent hydrogen atom, methyl or ethyl, R
7represent that carbon number is more than 2 and the alkylidene of the straight or branched of less than 4, X
1represent that oxygen atom or NH, n are-R
7the average addition molal quantity of-O-base, represent more than 50 and be less than 140 number.With regard to improve the dispersiveness of inorganic pigment and the viewpoint of improved sheet fissility and in copolymer the easiness of guiding structure unit (b) viewpoint with regard to, R
4and R
5be preferably hydrogen atom or methyl, be more preferably hydrogen atom, R
6be preferably hydrogen atom or methyl, be more preferably methyl, R
7be preferably ethylidene or propylidene, be more preferably ethylidene, R
8be preferably methyl or ethyl, be more preferably methyl, X
1be preferably oxygen atom.With regard to the raising dispersiveness of inorganic pigment and the viewpoint of improved sheet fissility, n is more than 50, be preferably more than 51, be more preferably more than 58, and then be preferably more than 72, and then be more preferably more than 88, and then be more preferably more than 110, with regard to the viewpoint of the easiness of manufacture, n is less than 140, is preferably less than 130.
As construction unit (b), can enumerate that to be derived from the monomer with nonionic base (following, also be called " monomer (b) ") construction unit or after polymerization, import nonionic base and the construction unit etc. that obtains, with regard to the viewpoint of the easiness of manufacture, be preferably derived from the construction unit of monomer (b).As nonionic base, include, for example the polyoxy alkylidene such as polyoxyethylene, polyoxypropylene.With regard to the viewpoint of easiness manufactured, construction unit (b) is preferably derived from can with the construction unit with the monomer of ethene unsaturated double-bond of monomer copolymerization forming construction unit (a).
As monomer (b), with regard to improve inorganic pigment dispersiveness, improve with regard to the stability of dispersion and the viewpoint of sheet fissility, be preferably monomer represented by formula (5).
[changing 6]
In formula (5), R
4, R
5, R
6, R
7, R
8, X
1and n is identical with said structure unit (b) in one or more embodiment.
As monomer (b), can enumerate: single (methyl) acrylate of methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group poly-(ethylene glycol/propylene glycol), ethyoxyl poly-(ethylene glycol/propylene glycol) single (methyl) acrylate, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, 2-methoxy ethyl (methyl) acrylamide, 2-ethoxyethyl group (methyl) acrylamide, 3-methoxy-propyl (methyl) acrylamide etc.In these, with regard to improving the viewpoint of the dispersiveness of inorganic pigment, the stability of dispersion and sheet fissility, be preferably methoxy poly (ethylene glycol) (methyl) acrylate, be more preferably methoxy polyethylene glycol methacrylate-styrene polymer.In this description, so-called " (methyl) acrylate ", means to be selected from least one in acrylate and methacrylate.Similarly, so-called " (methyl) acrylamide ", means to be selected from least one in acrylamide and Methacrylamide.
About the ratio of the construction unit (b) formed in the general construction unit of copolymer of the present invention, with regard to the raising dispersiveness of inorganic pigment and the viewpoint of improved sheet fissility, be more than 55 quality %, be preferably more than 60 quality %, be more preferably more than 65 quality %, with regard to identical viewpoint, be below 99 quality %, be preferably below 95 quality %, be more preferably below 87 quality %, and then be preferably below 80 quality %, and then be more preferably below 75 quality %.
About the mass ratio (construction unit (a)/construction unit (b)) of the construction unit (a) in copolymer of the present invention relative to construction unit (b), with regard to the raising dispersiveness of inorganic pigment and the viewpoint of fissility, be preferably more than 0.05, be more preferably more than 0.12, and then be preferably more than 0.16, and then be more preferably more than 0.19, with regard to improving the viewpoint of the dispersiveness of inorganic pigment, be preferably less than 0.50, be more preferably less than 0.35, and then be preferably less than 0.28, with regard to improving the viewpoint of fissility, and then be more preferably less than 0.24.
[construction unit (c)]
With regard to improving the viewpoint of dispersiveness, copolymer of the present invention is preferably also containing construction unit (c).The construction unit of construction unit (c) in one or more embodiment represented by formula (3).Construction unit (c) is hydrophobicity, thinks and can suppress copolymer stripping again in non-water solvent.
[changing 7]
In formula (3), R
9, R
10and R
11identical or different, represent hydrogen atom, methyl or ethyl, X
3represent oxygen atom or NH, R
12and R
13represent that carbon number is the alkyl of more than 1 and less than 30.With regard to improve inorganic pigment dispersiveness and in copolymer the easiness of guiding structure unit (c) viewpoint with regard to, R
9and R
10be preferably hydrogen atom or methyl, be more preferably hydrogen atom, R
11be preferably hydrogen atom or methyl, X
3be preferably oxygen atom, R
12be preferably alkyl or alkenyl, R
12carbon number be more than 1, be preferably less than 22, be more preferably less than 18.As R
12, can enumerate: methyl, ethyl, butyl, octyl group, 2-ethylhexyl, decyl, lauryl, myristyl, cetyl, stearyl, oleyl, Shan Yu base etc.With regard to identical viewpoint, R
13preferably phenyl or carbon number are the alkyl of more than 1 and less than 22.
As construction unit (c), the construction unit being derived from following monomer (c) can be enumerated, with regard to improving the viewpoint of dispersiveness and fissility, preferably be derived from the construction unit of (methyl) alkyl acrylate, be more preferably more than one the construction unit in the group being derived from and being selected from and being made up of methyl methacrylate, stearyl methacrylate and stearyl acrylate ester, and then be preferably derived from the construction unit of methyl methacrylate.
As construction unit (c), with regard to the viewpoint of the easiness of guiding structure unit (c) in copolymer, preferably be derived from the construction unit of the monomer (following, to be also called " monomer (c) ") represented by formula (6).
[changing 8]
In formula (6), R
9, R
10, R
11, R
12, R
13and X
3identical with said structure unit (c) in one or more embodiment.
As monomer (c), can enumerate: (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) acrylic acid Shan Yu ester; Alkyl (methyl) acrylamides such as butyl (methyl) acrylamide, octyl group (methyl) acrylamide, lauryl (methyl) acrylamide, stearyl (methyl) acrylamide, Shan Yu base (methyl) acrylamide; The alpha-olefins such as 1-decene, 1-octadecylene; And styrene etc.
In these, with regard to the viewpoint of dispersion stabilization, be preferably (methyl) alkyl acrylate and styrene, be more preferably (methyl) methyl acrylate and (methyl) stearyl acrylate ester, with regard to improving the viewpoint of dispersiveness and fissility, and then be preferably (methyl) methyl acrylate, and then be more preferably methyl methacrylate.
About the ratio of the construction unit (c) formed in the general construction unit of copolymer of the present invention, with regard to the raising dispersiveness of inorganic pigment and the viewpoint of improved sheet fissility, be preferably more than 0 quality %, be more preferably more than 3 quality %, be more preferably more than 8 quality %, and then be preferably more than 12 quality %, with regard to identical viewpoint, be preferably below 35 quality %, be more preferably below 25 quality %, and then be preferably below 18 quality %.
About the mass ratio (construction unit (c)/construction unit (b)) of the construction unit (c) in copolymer of the present invention relative to construction unit (b), with regard to improving the viewpoint of the dispersiveness of inorganic pigment, be preferably more than 0.05, be more preferably more than 0.06, and then be preferably more than 0.10, and then be more preferably more than 0.18, with regard to identical viewpoint, be preferably less than 0.70, be more preferably less than 0.60, and then be preferably less than 0.50, and then be more preferably less than 0.25.
[other construction units]
Copolymer of the present invention also can contain other construction units beyond expel stagnation structure unit (a), (b) and (c) in the scope not undermining effect of the present invention.With regard to showing the viewpoint of effect of the present invention, the ratio forming other construction units above-mentioned in the general construction unit of copolymer of the present invention is preferably below 10 quality %, is more preferably below 3 quality %, and then is preferably below 1 quality %.
[preparation of the copolymer in high-molecular dispersant for inorganic pigments]
Copolymers of the present invention as can by utilize solution polymerization process to make to comprise monomer (a), monomer (b), monomer (c) optionally the known method such as polymerizing monomer components and obtain.In one embodiment of the present invention, the mass ratio of construction unit (a) in general construction unit can be considered monomer (a) with after being polymerized can the addition total of the monomer of acidic groups that can neutralize relative to the mass ratio of the total monomer composition used in being polymerized.The mass ratio of construction unit (b) in general construction unit can be considered monomer (b) and can import the total of monomer of nonionic base relative to the mass ratio of the total monomer composition used in being polymerized after being polymerized.Relative to the mass ratio (construction unit (c)/construction unit (b)) of construction unit (b), construction unit (c) can be considered that hydrophobic monomer (c) in the total monomer composition used in polymerization is relative to monomer (b) and the mass ratio of total of monomer that can import nonionic base after being polymerized.Therefore, the present invention is the manufacture method of dispersant of the present invention in another mode, and this manufacture method comprises the steps: to make to comprise monomer (a) with the content of above-mentioned construction unit (a), (b), (c) optionally respectively or can the monomer of the addition acidic groups that can neutralize, monomer (b) or can import the monomer of nonionic base and the polymerizing monomer components of hydrophobic monomer (c) optionally after polymerization after polymerization.
As the solvent used in polymerisation in solution, include, for example: the aromatic hydrocarbon such as toluene, dimethylbenzene; The lower alcohols such as ethanol, 2-propyl alcohol; The ketone such as acetone, methyl ethyl ketone; The ether such as oxolane, diethylene glycol dimethyl ether.The amount of solvent is preferably more than 0.5 mass parts relative to total monomer 1 mass parts and below 10 mass parts.
As polymerization initiator, known radical polymerization initiator can be used, include, for example: azo system polymerization initiator, hydroperoxide type, dialkyl class, diacyl peroxides class, ketone peroxide class etc.The amount of polymerization initiator, relative to total monomer 100 moles, is preferably more than 1 mole, is more preferably more than 2 moles, and then is preferably more than 3 moles, is preferably less than 15 moles, is more preferably less than 12 moles, and then is preferably less than 9 moles.Polymerisation is preferable over nitrogen and flows down and carry out, and reaction temperature is preferably more than 60 DEG C and less than 180 DEG C, and the reaction time is preferably more than 0.5 hour and less than 20 hours.
Also and then polymerizable chain transfer agents can be added in time being polymerized.As the concrete example of polymerizable chain transfer agents, can enumerate: spicy thioalcohol, n-dodecyl mereaptan, tert-dodecyl mercaptan, positive tetradecanylthioalcohol, mercaptoethanol, 3-sulfydryl-thio-alcohol such as 1,2-PD, mercapto succinic acid; Thiuram-disulfide class; Hydro carbons; Unsaturated cyclic hydrocarbon compound; Unsaturated heterocycle shape compounds etc., these individually can use or mix two or more use.
In copolymer of the present invention, the arrangement of construction unit (a), construction unit (b), construction unit (c) can be any person in random, block or grafting.
About the weight average molecular weight of copolymer of the present invention, with regard to the raising dispersiveness of inorganic pigment and the viewpoint of improved sheet fissility, be preferably more than 1000, be more preferably more than 2000, and then be preferably more than 4000, with regard to identical viewpoint, be preferably less than 100000, be more preferably less than 50000, and then be preferably less than 30000, and then be more preferably less than 15000.Weight average molecular weight is the value recorded by GPC (GelPermeationChromatography, gel permeation chromatography), and the details of condition determination are as shown in the Examples.
About the copolymer manufactured in above-mentioned mode and/or high-molecular dispersant for inorganic pigments, the excellent dispersion of the inorganic pigment in non-water solvent, the dispersiveness of preferred alkaline inorganic pigment, dispersion stabilization and sheet fissility are excellent.Therefore, dispersant of the present invention is used for the dispersion of the inorganic pigment in non-water solvent, is preferably the dispersion for the basic mineral pigment in non-water solvent.
[non-water solvent]
About the solubility parameter (unit: [(MPa) of non-water solvent spendable in the present invention
1/2]), with regard to improve inorganic pigment dispersiveness and with the viewpoint of the compatibility of above-mentioned macromolecule dispersing agent with regard to, be preferably more than 20, be more preferably more than 21, be preferably less than 30, be more preferably less than 26.Above-mentioned solubility parameter refers to the value calculated by the method [R.F.Fedors.Polym.Eng.Sci., 14,147 (1974)] of Fedors.
Above-mentioned solubility parameter can suitably adjust by the two or more organic solvent of mixing.The solubility parameter of this kind of mixed solvent also can above method and obtaining, but as easy method, also can calculate according to the solubility parameter of each composition of mixed solvent and percentage by volume and obtain.Such as, when the situation mixed with percentage by volume 50:50 with ethanol by toluene, its solubility parameter is (18.3) × 0.5+ (26.2) × 0.5=22.3.
As non-water solvent spendable in the present invention, can enumerate in organic solvents such as being selected from dimethylbenzene (18.2), ethyl acetate (18.2), toluene (18.3), oxolane (18.5), methyl ethyl ketone (19.3), acetone (19.7), butyl cellosolve (20.2), dimethyl formamide (24.7), normal propyl alcohol (24.9), ethanol (26.2), dimethyl sulfoxide (DMSO) (26.4), n-butanol (28.7), methyl alcohol (29.7) more than one.Numerical value in () is solubility parameter.
[inorganic pigment]
Usually, the surface of inorganic pigment has sour point, both alkali points.Acid in non-water solvent and the intensity of alkali can be obtained by back titration method, and the inorganic pigment that can identify for dispersion is acid or is alkalescence.So-called back titration method, refer to following method: mixed with inorganic pigment with certain ratio by the alkaline reagent (or acid reagent) of concentration known in advance, after making it neutralize fully, centrifugal separator etc. is utilized to make its Separation of Solid and Liquid, and its supernatant of titration, obtain acid amount (or alkali number) according to the amount (or amount of acid reagent) of reduced alkaline reagent.In the present invention, alkali number and acid amount are for obtaining by following method.
1) computation of alkali number
Precise is as the inorganic pigment 2g of sample, be added in 1/100N acetic acid-toluene/ethanol (volume ratio 48:52) solution 30mL, utilize ultrasonic cleaner (" 1510J-MT " that Branson company manufactures) to carry out 1 hour dispersion treatment, and obtain dispersion liquid.In leaving standstill after 24 hours, use centrifugal separator (" CP-56G " that Hitachi, Ltd manufactures), under 25,000rpm, the condition of 60 minutes, by a part of Separation of Solid and Liquid of dispersion liquid.Be separated liquid portion 10mL is added to after in toluene/ethanol solvent (volume ratio 2:1) 20mL being added with phenolphthalein indicator, utilizes 1/100N potassium hydroxide-ethanol solution to carry out acid-base titration.If titer is now set to XmL, by and 1/100N acetic acid-toluene/ethanol (volume ratio 48:52) solution 10mL needed for titer be set to BmL, the amount of sample is set to Sg, then utilizes following formula to obtain alkali number.
Alkali number (μm ol/g)=30 × (B-X)/S
2) computation of acid amount
Precise is as the inorganic pigment 2g of sample, be added in 1/100N n-butylamine-toluene/ethanol (volume ratio 48:52) solution 30mL, utilize ultrasonic cleaner (" 1510J-MT " that Branson company manufactures) to carry out 1 hour dispersion treatment, and obtain dispersion liquid.In leaving standstill after 24 hours, use centrifugal separator (" CP-56G " that Hitachi, Ltd manufactures), under 25,000rpm, the condition of 60 minutes, by a part of Separation of Solid and Liquid of dispersion liquid.Be separated liquid portion 10mL is added to after in toluene/ethanol solvent (volume ratio 2:1) 20mL being added with bromocresol green indicator, utilizes 1/100N hydrochloric acid-ethanolic solution to carry out acid-base titration.If titer is now set to XmL, by and 1/100N n-butylamine-toluene/ethanol (volume ratio 48:52) solution 10mL needed for titer be set to BmL, the amount of sample is set to Sg, then utilize following formula obtain acid amount.
Acid amount (μm ol/g)=30 × (B-X)/S
In the present invention, with regard to the raising dispersiveness of inorganic pigment and the viewpoint of improved sheet fissility, inorganic pigment is preferably basic mineral pigment.So-called basic mineral pigment, refers to that alkali number defined above has the inorganic compound of the value being greater than acid amount defined above, specifically, can enumerate: the metal oxides such as titanium oxide, magnesia, barium monoxide, aluminium oxide; The metal carbonate such as magnesium carbonate, brium carbonate; The composite oxides such as barium zirconate, calcium zirconate, calcium titanate, barium titanate, strontium titanates, are preferably selected from more than one the pigment in the group be made up of magnesia, brium carbonate, titanium oxide, calcium titanate, barium titanate, barium zirconate and calcium zirconate.As the basic mineral pigment in the present invention, with regard to improving the viewpoint of the characteristic of potsherd, be more preferably above-mentioned composite oxides, and then be preferably barium titanate.
About can use aptly the inorganic pigment of dispersant of the present invention based on BET (Brunauer-Emmett-Teller, Bu Ete) average grain diameter of specific area is (following, also be called " BET average grain diameter "), and in paste compound of the present invention contained inorganic pigment utilize the average grain diameter of dynamic light scattering method (following, also be called " D50 "), with regard to improving the viewpoint of dispersiveness, be preferably below 500nm, be more preferably below 200nm, and then be preferably below 100nm, with regard to maintaining the viewpoint of dispersiveness, be preferably more than 5nm, be more preferably more than 7nm, and then be preferably more than 8nm.Above-mentioned D50 is the channel zapping of the scattering strength of principle based on following dynamic light scattering method is the particle diameter of 50%, can measure by the method recorded in embodiment.The BET average grain diameter of inorganic pigment is preferably the average grain diameter of pulverous inorganic pigment, calculates in following mode.
(calculation method of the BET average grain diameter of inorganic pigment)
The BET average grain diameter of inorganic pigment can suppose that inorganic pigment particles is the ball of particle diameter R (m), uses the BET specific surface area S (m recorded by nitrogen adsorption method
2/ g), the proportion ρ (g/cm of inorganic pigment particles
3) and obtain.That is, because BET specific surface area is the surface area of per unit mass, if so surface area is set to A (m
2), the quality of particle is set to W (g), then obtains following relational expression.
S(m
2/g)＝A(m
2)/W(g)
＝[4×π×(R/2)
2]/[4/3×π×(R/2)
3×ρ×10
6]
＝6/(R×ρ×10
6)
If change the unit of particle diameter, then become following formula, BET average grain diameter can be obtained.
R(nm)＝6000/(S×ρ)
Such as, if the BET specific surface area of barium titanate (proportion 6.0) is 5.0 (m
2/ g), then its BET average grain diameter is 200nm.
[process for dispersing]
Another mode of the present invention is a kind of process for dispersing, and it comprises use dispersant of the present invention and makes the step that inorganic pigment disperses in non-water solvent.Above-mentioned dispersion steps such as comprises the steps: basic mineral pigment, dispersant of the present invention and non-water solvent to mix, and preferably together mixes with zirconium oxide bead.The inorganic pigment of mixing and the amount of dispersant of the present invention can be set in the scope of the content of each composition in following paste compound.According to process for dispersing of the present invention, inorganic pigment can be made to be dispersed in non-water solvent imperceptibly, following paste compound can be manufactured.Therefore, which of the present invention is a kind of manufacture method of paste compound, and it comprises use dispersant of the present invention and makes the step that inorganic pigment disperses in non-water solvent.
[paste compound]
If use dispersant of the present invention, then can obtain inorganic pigment and be dispersed in paste compound in non-water solvent.Therefore, the present invention can provide a kind of paste compound in another mode, and it contains non-water solvent, inorganic pigment and macromolecule dispersing agent, and above-mentioned macromolecule dispersing agent is dispersant of the present invention or copolymer.According to paste compound of the present invention, as described below, the fine dispersion of inorganic pigment can be realized aptly.
About the content of the inorganic pigment in paste compound, with regard to improving the viewpoint of dispersiveness, be preferably more than 5 quality %, be more preferably more than 10 quality %, with regard to identical viewpoint, be preferably below 60 quality %, be more preferably below 50 quality %.Copolymer of the present invention is different according to the particle diameter of inorganic pigment relative to the content of inorganic pigment 100 mass parts, such as in time using BET average grain diameter to be the situation of the inorganic pigment of 10 ~ 500nm, be preferably more than 0.1 mass parts, be more preferably more than 0.2 mass parts, with regard to identical viewpoint, be preferably below 10 mass parts, be more preferably below 5 mass parts.
The evaluation Example of the dispersiveness in dispersion liquid and slurry as also can by measuring slurry viscosity, measure sedimentation time of the inorganic pigment through dispersion etc. and evaluate, if but the size distribution of inorganic pigment in slurry is the primary particle size person close to this inorganic pigment powder, then slurry viscosity step-down, sedimentation time is also elongated, according to as above opinion, in the present invention, can evaluate by the size distribution of the inorganic pigment measured in slurry.Specifically, can evaluate as described in embodiment.
[other compositions in paste compound]
Paste compound of the present invention also can containing additives such as low molecular compound such as resin glue, antistatic additive, plasticizer, lubricant, dispersing aid such as polyvinyl acetal resins in the scope not undermining effect of the present invention.
As above-mentioned resin glue, with regard to improved sheet fissility and improve potsherd performance viewpoint with regard to, be preferably polyvinyl acetal resin, be more preferably polyvinyl butyral resin.About the acetalizing degree of above-mentioned polyvinyl acetal resin, with regard to improving the flexual viewpoint of dissolubility in non-water solvent and potsherd, be preferably more than 55 % by mole, be more preferably more than 65 % by mole, with regard to improving the viewpoint of the intensity of potsherd, be preferably less than 80 % by mole, be more preferably less than 75 % by mole.
About the content of the resin glue in paste compound of the present invention relative to inorganic pigment 100 mass parts, with regard to the viewpoint of the intensity of improved sheet fissility and potsherd, be preferably more than 2 mass parts, be more preferably more than 4 mass parts, and then be preferably more than 6 mass parts, with regard to sheet fissility and formed potsherd easiness viewpoint with regard to, be preferably below 20 mass parts, be more preferably below 18 mass parts, and then be preferably below 16 mass parts, and then be more preferably below 11 mass parts, and then be more preferably below 9 mass parts.
As above-mentioned plasticizer, can enumerate: the aklylene glycol diester etc. such as the di adipates such as phthalic acid two (2-ethylhexyl) ditridecyl phthalate such as ester, dibutyl phthalate, adipic acid (2-ethylhexyl) ester, triethylene glycol two (2-ethylhexyl) ester, with regard to low volatility and improve potsherd flexibility viewpoint with regard to, be preferably phthalic acid two (2-ethylhexyl) ester.About the content of the plasticizer in paste compound of the present invention relative to inorganic pigment 100 mass parts, with regard to the viewpoint of the performance of improved sheet fissility and potsherd, be preferably more than 0.05 mass parts, be more preferably more than 0.1 mass parts, with regard to maintaining the viewpoint of the intensity of potsherd, be preferably below 15.0 mass parts, be more preferably below 10.0 mass parts.
As above-mentioned antistatic additive, with regard to improving the viewpoint of fissility, be preferably cationic antistatic additive.As above-mentioned cationic antistatic additive, include, for example alkyl imidazoline, alkyl imidazole etc. and there is nitrogenous heterocyclic compound.About the content of the antistatic additive in paste compound of the present invention relative to inorganic pigment 100 mass parts, with regard to the viewpoint of the performance of improved sheet fissility and potsherd, be preferably more than 0.05 mass parts, be more preferably more than 0.1 mass parts, with regard to maintaining the viewpoint of the intensity of potsherd, be preferably below 2.0 mass parts, be more preferably below 1.5 mass parts.
About above-mentioned embodiment, the present invention and then disclose following composition, manufacture method or purposes.
< 1 > high-molecular dispersant for inorganic pigments, it to be included in general construction unit containing more than construction unit (a) 1 quality % represented by formula (1) and below 45 quality % and more than construction unit (b) the 55 quality % represented by formula (2) and the copolymer of below 99 quality %, and use in non-water solvent
[changing 9]
[in formula (1), R
1, R
2and R
3identical or different, represent hydrogen atom, methyl or ethyl, M represents hydrogen atom or cation.]
[changing 10]
[in formula (2), R
4, R
5, R
6and R
8identical or different, represent hydrogen atom, methyl or ethyl, R
7represent that carbon number is more than 2 and the alkylidene of the straight or branched of less than 4, X
1represent that oxygen atom or NH, n are-R
7the average addition molal quantity of-O-base, represent more than 50 and be less than 140 number.]
< 2 > as the high-molecular dispersant for inorganic pigments of < 1 >, the R of its Chinese style (1)
1and R
2be preferably hydrogen atom or methyl, be more preferably hydrogen atom.
< 3 > as the high-molecular dispersant for inorganic pigments of < 1 > or < 2 >, the R of its Chinese style (1)
3be preferably hydrogen atom or methyl, be more preferably methyl.
The high-molecular dispersant for inorganic pigments of < 4 > any one of < 1 > to < 3 >, the M of its Chinese style (1) is preferably ammonium, organic ammonium or hydrogen atom, is more preferably hydrogen atom.
The high-molecular dispersant for inorganic pigments of < 5 > any one of < 1 > to < 4 >, the ratio wherein forming the construction unit (a) in the general construction unit of copolymer is more than 1 quality %, be preferably more than 3 quality %, be more preferably more than 5 quality %, and then be preferably more than 8 quality %, and then be preferably more than 12 quality %.
The high-molecular dispersant for inorganic pigments of < 6 > any one of < 1 > to < 5 >, the ratio wherein forming the construction unit (a) in the general construction unit of copolymer is below 45 quality %, be preferably below 35 quality %, be more preferably below 24 quality %, and then be preferably below 18 quality %.
The high-molecular dispersant for inorganic pigments of < 7 > any one of < 1 > to < 6 >, wherein construction unit (a) is preferably derived from more than one the construction unit in the group being selected from and being made up of acrylic acid and methacrylic acid.
The high-molecular dispersant for inorganic pigments of < 8 > any one of < 1 > to < 7 >, the R of its Chinese style (2)
4and R
5be preferably hydrogen atom or methyl, be more preferably hydrogen atom.
The high-molecular dispersant for inorganic pigments of < 9 > any one of < 1 > to < 8 >, the R of its Chinese style (2)
6be preferably hydrogen atom or methyl, be more preferably methyl.
The high-molecular dispersant for inorganic pigments of < 10 > any one of < 1 > to < 9 >, the R of its Chinese style (2)
7be preferably ethylidene or propylidene, be more preferably ethylidene.
The high-molecular dispersant for inorganic pigments of < 11 > any one of < 1 > to < 10 >, the R of its Chinese style (2)
8be preferably methyl or ethyl, be more preferably methyl.
The high-molecular dispersant for inorganic pigments of < 12 > any one of < 1 > to < 11 >, the X of its Chinese style (2)
1be preferably oxygen atom.
The high-molecular dispersant for inorganic pigments of < 13 > any one of < 1 > to < 12 >, the n of its Chinese style (2) is more than 50, be preferably more than 51, be more preferably more than 58, and then be preferably more than 72, and then be more preferably more than 88, and then be more preferably more than 110.
The high-molecular dispersant for inorganic pigments of < 14 > any one of < 1 > to < 13 >, the n of its Chinese style (2) is less than 140, is preferably less than 130.
The high-molecular dispersant for inorganic pigments of < 15 > any one of < 1 > to < 14 >, the ratio wherein forming the construction unit (b) in the general construction unit of copolymer is more than 55 quality %, be preferably more than 60 quality %, be more preferably more than 65 quality %.
The high-molecular dispersant for inorganic pigments of < 16 > any one of < 1 > to < 15 >, the ratio wherein forming the construction unit (b) in the general construction unit of copolymer is below 99 quality %, be preferably below 95 quality %, be more preferably below 87 quality %, and then be preferably below 80 quality %, and then be more preferably below 75 quality %.
The high-molecular dispersant for inorganic pigments of < 17 > any one of < 1 > to < 16 >, the construction unit (a) wherein forming copolymer is preferably more than 0.05 relative to the mass ratio (construction unit (a)/construction unit (b)) of construction unit (b), be more preferably more than 0.12, and then be preferably more than 0.16, and then be more preferably more than 0.19, be preferably less than 0.50, be more preferably less than 0.35, and then be preferably less than 0.28, and then be more preferably less than 0.24.
The high-molecular dispersant for inorganic pigments of < 18 > any one of < 1 > to < 17 >, it is preferably also containing the construction unit (c) represented by formula (3)
[changing 11]
[in formula (3), R
9, R
10, and R
11identical or different, represent hydrogen atom, methyl or ethyl, X
3represent oxygen atom or NH, R
12and R
13represent that carbon number is the alkyl of more than 1 and less than 30.]
< 19 > is as the high-molecular dispersant for inorganic pigments of < 18 >, and wherein construction unit (c) is preferably more than 0.05 and less than 0.70 relative to the mass ratio ((c)/(b)) of construction unit (b).
< 20 > as the high-molecular dispersant for inorganic pigments of < 18 > or < 19 >, the R of its Chinese style (3)
9and R
10be preferably hydrogen atom or methyl, be more preferably hydrogen atom.
The high-molecular dispersant for inorganic pigments of < 21 > any one of < 18 > to < 20 >, the R of its Chinese style (3)
11be preferably hydrogen atom or methyl.
The high-molecular dispersant for inorganic pigments of < 22 > any one of < 18 > to < 21 >, the X of its Chinese style (3)
3be preferably oxygen atom.
The high-molecular dispersant for inorganic pigments of < 23 > any one of < 18 > to < 22 >, the R of its Chinese style (3)
12be preferably alkyl or alkenyl.
The high-molecular dispersant for inorganic pigments of < 24 > any one of < 18 > to < 23 >, the R of its Chinese style (3)
12carbon number be more than 1, be preferably less than 22, be more preferably less than 18.
The high-molecular dispersant for inorganic pigments of < 25 > any one of < 18 > to < 24 >, the R of its Chinese style (3)
12be preferably methyl, ethyl, butyl, octyl group, 2-ethylhexyl, decyl, lauryl, myristyl, cetyl, stearyl, oleyl Huo Shan Yu base.
The high-molecular dispersant for inorganic pigments of < 26 > any one of < 18 > to < 25 >, the R of its Chinese style (3)
13preferably phenyl or carbon number are the alkyl of more than 1 and less than 22.
The high-molecular dispersant for inorganic pigments of < 27 > any one of < 18 > to < 26 >, the ratio wherein forming the construction unit (c) in the general construction unit of copolymer is preferably more than 0 quality %, be more preferably more than 3 quality %, be more preferably more than 8 quality %, and then be preferably more than 12 quality %.
The high-molecular dispersant for inorganic pigments of < 28 > any one of < 18 > to < 27 >, the ratio wherein forming the construction unit (c) in the general construction unit of copolymer is preferably below 35 quality %, be more preferably below 25 quality %, and then be preferably below 18 quality %.
The high-molecular dispersant for inorganic pigments of < 29 > any one of < 18 > to < 28 >, construction unit (c) wherein in copolymer is preferably more than 0.05 relative to the mass ratio (construction unit (c)/construction unit (b)) of construction unit (b), be more preferably more than 0.06, and then be preferably more than 0.10, and then be more preferably more than 0.18.
The high-molecular dispersant for inorganic pigments of < 30 > any one of < 18 > to < 29 >, construction unit (c) wherein in copolymer is preferably less than 0.70 relative to the mass ratio (construction unit (c)/construction unit (b)) of construction unit (b), be more preferably less than 0.60, and then be preferably less than 0.50, and then be more preferably less than 0.25.
The high-molecular dispersant for inorganic pigments of < 31 > any one of < 18 > to < 30 >, wherein construction unit (c) is preferably derived from the construction unit of (methyl) alkyl acrylate, be more preferably more than one the construction unit in the group being derived from and being selected from and being made up of methyl methacrylate, stearyl methacrylate and stearyl acrylate ester, and then be preferably derived from the construction unit of methyl methacrylate.
The high-molecular dispersant for inorganic pigments of < 32 > any one of < 1 > to < 31 >, wherein the weight average molecular weight of copolymer is preferably more than 1000, be more preferably more than 2000, and then be preferably more than 4000.
The high-molecular dispersant for inorganic pigments of < 33 > any one of < 1 > to < 32 >, wherein the weight average molecular weight of copolymer is preferably less than 100000, be more preferably less than 50000, and then be preferably less than 30000, and then be more preferably less than 15000.
< 34 > process for dispersing, it uses the high-molecular dispersant for inorganic pigments any one of < 1 > to < 33 > and basic mineral pigment is disperseed.
< 35 > paste compound, it contains non-water solvent, basic mineral pigment and the high-molecular dispersant for inorganic pigments any one of < 1 > to < 33 >.
< 36 > is as the paste compound of < 35 >, wherein basic mineral pigment is preferably selected from more than one the pigment in the group be made up of magnesia, brium carbonate, titanium oxide, calcium titanate, barium titanate, barium zirconate and calcium zirconate, is more preferably barium titanate.
< 37 > is as the paste compound of < 35 > or < 36 >, the content of the inorganic pigment wherein in paste compound is preferably more than 5 quality %, be more preferably more than 10 quality %, be preferably below 60 quality %, be more preferably below 50 quality %.
The paste compound of < 38 > any one of < 35 > to < 37 >, wherein in time using BET average grain diameter to be the situation of the inorganic pigment of 10 ~ 500nm, copolymer any one of < 1 > to < 33 > is preferably more than 0.1 mass parts relative to the content of inorganic pigment 100 mass parts, be more preferably more than 0.2 mass parts, be preferably below 10 mass parts, be more preferably below 5 mass parts.
The paste compound of < 39 > any one of < 35 > to < 38 >, it is preferably also containing polyvinyl acetal resin, more preferably containing polyvinyl butyral resin.
The paste compound of < 40 > any one of < 35 > to < 39 >, it is dispersed in non-water solvent for making inorganic pigment.
The purposes of the high-molecular dispersant for inorganic pigments any one of < 41 > < 1 > to < 33 >, this high-molecular dispersant for inorganic pigments is in order to manufacture potsherd.
The purposes of the paste compound any one of < 42 > < 35 > to < 39 >, this paste compound is in order to manufacture potsherd.
Embodiment
Below, by embodiment, the present invention is described.In following embodiment, the X be designated as in " PAG (X mole) " represents the average addition molal quantity of the alkylene oxide of this aklylene glycol.The mensuration of the particle diameter of weight average molecular weight, solid content composition and paste compound and the evaluation of sheet fissility are undertaken by following methods.
(1) mensuration of weight average molecular weight
Use gel permeation chromatography (following, to be also called " GPC ") method.Utilize DMF to dilute sample, the solid content constituent concentration preparing sample be the solution of 0.3 quality % as sample solution, and its 100 μ L is provided with measure.N is dissolved in the mode of the concentration becoming 60mmol/L and 50mmol/L respectively by making phosphoric acid and lithium bromide, in dinethylformamide, the solution of gained is as eluent, and by GPC [device: " HLC-8120GPC " that Dong Cao limited company manufactures, detector: Differential refractometer (device is subsidiary), post: " TSK-GEL α-M " that Dong Cao limited company manufactures × 2, column temperature: 40 DEG C, eluent flow rate: 1mL/min], measure.As standard substance, (Dong Cao limited company manufactures, molecular weight 5.26 × 10 to use polystyrene
2, 1.02 × 10
5, 8.42 × 10
6, Xi Wei Industries, Inc manufactures: molecular weight 4.0 × 10
3, 3.0 × 10
4, 9.0 × 10
5).
(2) mensuration of solid content composition
In culture dish, put into glass bar and drying anhydrous sodium sulfate 10g, measure sample 1g and be placed in one, and utilize glass bar to mix, utilize the pressure Reduction Dryer (pressure 8kPa) of 105 DEG C dry 2 hours.Weigh dried quality, using the value that obtains by following formula as solid content composition.
Solid content composition (quality %)={ quality of [(dried quality-(quality of the weight+anhydrous sodium sulfate of the weight+glass bar of culture dish))]/sample } × 100
(3) mensuration of the particle diameter of paste compound
As particle size determination device, use the particle size distribution machine (" ZetasizerNanoZS " that Sysmex company manufactures) of the principle based on photon correlation method (dynamic light scattering method).Using mixing non-aqueous slurry composition 0.025g and the toluene/ethanol mixed solvent (volume ratio: 48/52) 2mL and the solution that obtains are as sample as decentralized medium.Be in the glass dish of 10mm in optical path length, get said sample 1.2mL, put into determination part, as location parameter, the input refractive index of particle, the refractive index of decentralized medium and sample viscosity measure.Such as when inorganic pigment is the situation of barium titanate, the refractive index of particle is set to 2.40.The refractive index of decentralized medium is set to 1.423, sample viscosity is set to 0.752.The particle diameter that the channel zapping of scattering strength becomes 50% is set to D50, the particle diameter that the channel zapping of scattering strength becomes 90% is set to D90.
(4) evaluation of sheet fissility
Use film dressing device (50 μm, gap), in the upper coating sizing-agent composition of mold release film (Di Ren film company of Du Pont manufacture " PurexA31 ") through silicone-treated, and at 60 DEG C dry 16 hours, and the potsherd that is shaped.The thickness of dried potsherd is 5 ~ 8 μm.By obtained potsherd and above-mentioned mold release film, together severing is minor face 4cm, the size of long limit 10cm obtains test film, make with the face opposite side being coated with paste compound (mold release film side) down, on the base of the desktop microtest machine (company of Shimadzu Seisakusho Ltd. manufacture " AutographAGS-X ") using two-sided tape to be fixed on by test film to be provided with 90 degree of disbonded test fixtures.Then, after 1cm is peeled off in one end of the potsherd of the short brink of test film in mold release film, utilize fixture to clamp, fixture is fixed on load unit (ロ ー De セ Le).Thereafter, make load unit increase with the speed of 1cm/ second and carry out 90 degree of strippings, using after load unit rising 3cm till rising 6cm during to the mean value of the load that load unit applies as peeling force.Peeling force is less, and fissility is better.
The details of the macromolecule dispersing agent used in embodiment and comparative example are shown in table 1.Herein, the abbreviation of the raw material used in table 1 and following embodiment is as described below.
MMA: methyl methacrylate (manufacture of gas chemical company of Mitsubishi)
SMA: stearyl methacrylate (" NKEsterS " that chemical industrial company of Xin Zhong village manufactures)
● SA: stearyl acrylate ester (" STA " that Osaka Organic Chemical Industry company manufactures)
PEG (45) MA: methoxy poly (ethylene glycol) (45 moles) methacrylate (" NK-EsterM-450G " that chemical industrial company of Xin Zhong village manufactures)
PEG (60) MA: methoxy poly (ethylene glycol) (60 moles) methacrylate (" ME-260 " that Dong Bang chemical industrial company manufactures)
PEG (74) MA: methoxy poly (ethylene glycol) (74 moles) methacrylate (" ME-320 " that Dong Bang chemical industrial company manufactures)
PEG (90) MA: methoxy poly (ethylene glycol) (90 moles) methacrylate (" BlemmerPME-4000 " that You company manufactures)
PEG (120) MA: methoxy poly (ethylene glycol) (120 moles) methacrylate (KAO. Corp. SA manufactures, production code member: chemical industry goods intermediate)
● MAA: methacrylic acid (" GE-110 " that gas chemical company of Mitsubishi manufactures)
AA: acrylic acid (manufacturing with light pure pharmaceutical worker's industry company)
MPD:3-sulfydryl-1,2-PD (" 1-thioglycerin " that rising sun chemical industrial company manufactures)
V-65B:2,2'-azo two (2,4-methyl pentane nitrile) (manufacturing with light pure pharmaceutical worker's industry company)
[embodiment 1]
In being provided with return duct, agitating device, temperature take into account in the detachable flask of 1L of nitrogen ingress pipe, add MAA6.75g, PEG (60) MA31.5g, MMA6.75g, the MPD1.8g as " initial interpolation monomer " and ethanol (An Tian chemical company manufacture, reagent) 27.0g, one side stirs in flask, one side carries out nitrogen displacement, and is warming up to 80 DEG C.One side stirs at 80 DEG C in flask, one side will be added in flask as the V-65B1.35g of " initator liquid " and the mixed liquor of ethanol 12.15g, then, lasting 3 hours by as MMA60.75g, PEG (60) MA283.5g, MAA60.75g, MPD16.2g, V-65B12.15g of " dropping monomer liquid " and the mixed liquor of ethanol 243.0g drops in flask.And then, stir 3 hours at 80 DEG C, and cool.Ethanol is added into adjust concentration in flask, thus obtains macromolecule dispersing agent solution.Solid content composition is 55.8 quality %, and weight average molecular weight is 8718.
[embodiment 2 ~ 14, comparative example 1 ~ 3]
Record respectively according to table 1 is changed " initial interpolation monomer ", the composition of " initator liquid " and " dropping monomer liquid ", in addition, by the method identical with embodiment 1, obtains macromolecule dispersing agent solution.Solid content composition and weight average molecular weight are as shown in table 1.
Table 1
[table 1]
(preparation method of paste compound)
By barium titanate powder, (BET specific surface area is 15m
2/ g) the toluene/ethanol mixed solvent (volume ratio: the capacity that 48/52) is added into is in the polyethylene container of 100mL of 36g, macromolecule dispersing agent 0.6g (solid content composition), diameter to be the content of barium titanate in the zirconium oxide bead 50g of 1mm and composition except zirconium oxide bead the be amount of 50 quality %, use desktop ball mill (" BIG-ROTORBR-2 " that ASONE company manufactures), under the condition of room temperature, 120r/min, carry out 96 hours dispersion treatment.Then, by polyvinyl butyral resin (" S-LECBM-1 " that ponding chemical industrial company manufactures, butyralization degree is 65 % by mole, amount of hydroxyl groups is 34 % by mole, molecular weight is about 40,000) 2.8g, phthalic acid two (2-ethylhexyl) ester 0.56g, alkyl imidazoline (" HomogenolL-95 " that KAO. Corp. SA manufactures) 0.2g, and make the content of barium titanate become the toluene/ethanol mixed solvent (volume ratio: 48/52) be added in said vesse of the amount of 30 quality % relative to paste compound, use above-mentioned desktop ball mill, in room temperature, 2 hours dispersion treatment are carried out under the condition of 120r/min.Utilize 200 object nylon filter removing zirconium oxide beads, and obtain paste compound.
(evaluation of dispersiveness and sheet fissility)
Use the paste compound obtained, carry out the mensuration of particle diameter (D50 and D90) and the evaluation of sheet fissility.Show the result in table 2.
[table 2]
[table 2]
As shown in table 2, the dispersiveness of the paste compound of embodiment 1 ~ 14 is the degree identical with comparative example 1 or 2, or more excellent, and the potsherd obtained by the paste compound of embodiment 1 ~ 14 demonstrates the fissility compared with comparative example 1 ~ 3 excellence.
[utilizability in industry]
As mentioned above, the present invention such as the manufacturing step of the paste compound containing the basic mineral pigment in non-water solvent and the manufacturing step of potsherd useful.
Claims (17)
1. a high-molecular dispersant for inorganic pigments, it to be included in general construction unit containing more than construction unit (a) 1 quality % represented by formula (1) and below 45 quality % and more than construction unit (b) the 55 quality % represented by formula (2) and the copolymer of below 99 quality %, and use in non-water solvent
In formula (1), R
1, R
2and R
3identical or different, represent hydrogen atom, methyl or ethyl, M represents hydrogen atom or cation,
In formula (2), R
4, R
5, R
6and R
8identical or different, represent hydrogen atom, methyl or ethyl, R
7represent that carbon number is more than 2 and the alkylidene of the straight or branched of less than 4, X
1represent that oxygen atom or NH, n are-R
7the average addition molal quantity of-O-base, represent more than 50 and be less than 140 number.
2. high-molecular dispersant for inorganic pigments as claimed in claim 1, wherein,
Described copolymer is contain more than construction unit (b) 55 quality % and the copolymer of below 95 quality % in general construction unit.
3., as the high-molecular dispersant for inorganic pigments of claim 1 or 2, it is also containing the construction unit (c) represented by formula (3),
In formula (3), R
9, R
10and R
11identical or different, represent hydrogen atom, methyl or ethyl, X
3represent oxygen atom or NH, R
12and R
13represent that carbon number is the alkyl of more than 1 and less than 30.
4. as the high-molecular dispersant for inorganic pigments of claim 1 or 2, it is also containing the construction unit (c) represented by formula (3), and construction unit (c) is more than 0.05 relative to mass ratio (c)/(b) of construction unit (b) and less than 0.70
In formula (3), R
9, R
10and R
11identical or different, represent hydrogen atom, methyl or ethyl, X
3represent oxygen atom or NH, R
12and R
13represent that carbon number is the alkyl of more than 1 and less than 30.
5. the high-molecular dispersant for inorganic pigments any one of Claims 1-4, wherein,
The R of formula (2)
7for ethylidene.
6. the high-molecular dispersant for inorganic pigments any one of claim 1 to 5, wherein,
Construction unit (a) is for being derived from more than one the construction unit in the group that is selected from and is made up of acrylic acid and methacrylic acid.
7. the high-molecular dispersant for inorganic pigments any one of claim 1 to 6, wherein,
The weight average molecular weight of described copolymer is more than 1000 and less than 100000.
8. the high-molecular dispersant for inorganic pigments any one of claim 1 to 7, wherein,
The construction unit (a) forming described copolymer is more than 0.05 relative to the mass ratio of construction unit (b) and construction unit (a)/construction unit (b) and less than 0.50.
9. the high-molecular dispersant for inorganic pigments any one of claim 3 to 8, wherein,
R in formula (3)
9and R
10for hydrogen atom.
10. the high-molecular dispersant for inorganic pigments any one of claim 3 to 9, wherein,
Construction unit (c) is for being derived from the construction unit of (methyl) alkyl acrylate.
11. high-molecular dispersant for inorganic pigments any one of claim 3 to 10, wherein,
Construction unit (c) is for being derived from more than one the construction unit in the group that is selected from and is made up of methyl methacrylate, stearyl methacrylate and stearyl acrylate ester.
12. high-molecular dispersant for inorganic pigments any one of claim 1 to 11, wherein,
R in formula (2)
4and R
5for hydrogen atom.
13. 1 kinds of process for dispersing, it uses the high-molecular dispersant for inorganic pigments any one of claim 1 to 12 to disperse basic mineral pigment.
14. 1 kinds of paste compounds, it contains non-water solvent, basic mineral pigment and the high-molecular dispersant for inorganic pigments any one of claim 1 to 12.
15. as the paste compound of claim 14, and it is also containing polyvinyl acetal resin.
16. as the paste compound of claims 14 or 15, wherein,
Basic mineral pigment is for being selected from the pigment in the group that is made up of magnesia, brium carbonate, titanium oxide, calcium titanate, barium titanate, barium zirconate and calcium zirconate.
The purposes of the dispersant any one of 17. claims 1 to 12, this dispersant is dispersed in non-water solvent in order to make inorganic pigment.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-192586 | 2013-09-18 | ||
| JP2013192586 | 2013-09-18 | ||
| PCT/JP2014/074492 WO2015041226A1 (en) | 2013-09-18 | 2014-09-17 | Polymer dispersant for inorganic pigment |
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|---|---|
| JP (1) | JPWO2015041226A1 (en) |
| KR (1) | KR20160054563A (en) |
| CN (1) | CN105517698A (en) |
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| JP5764960B2 (en) * | 2011-02-15 | 2015-08-19 | 日油株式会社 | Dispersant for carbon material, carbon material dispersion and carbon material composition |
| WO2016143563A1 (en) * | 2015-03-10 | 2016-09-15 | 花王株式会社 | High-molecular dispersant for inorganic pigments |
| KR102307035B1 (en) * | 2019-06-26 | 2021-09-29 | 양유경 | Sidewalk block combined with ceramic art tile and method for manufacturing thereof |
| JP7510169B2 (en) | 2020-12-25 | 2024-07-03 | サンノプコ株式会社 | Dispersants for non-aqueous coating agents and non-aqueous coating agents |
| CN115785324A (en) * | 2023-02-09 | 2023-03-14 | 广东壮丽彩印股份有限公司 | Preparation method of dispersing agent for nano calcium carbonate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1205619C (en) * | 1999-10-20 | 2005-06-08 | 株式会社村田制作所 | Ceramic paste composition and method of making ceramic blank sheet and multilayer electron element |
| US20090258975A1 (en) * | 2006-03-15 | 2009-10-15 | Kao Corporation | Nonaqueous pigment dispersion composition |
| CN102131574A (en) * | 2008-08-27 | 2011-07-20 | 花王株式会社 | High-molecular dispersant for inorganic pigments |
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| JPH01254237A (en) * | 1988-04-01 | 1989-10-11 | Lion Corp | Dispersant for organic solvent |
| JPH0672759A (en) * | 1991-07-30 | 1994-03-15 | Lion Corp | Binder for molding ceramic |
| JP2974617B2 (en) * | 1996-08-19 | 1999-11-10 | 花王株式会社 | Method for producing water-based ink for inkjet recording |
| JP3970597B2 (en) * | 2001-12-12 | 2007-09-05 | 株式会社日本触媒 | Inorganic pigment dispersant and paper coating pigment dispersion |
| JP5368023B2 (en) * | 2007-07-23 | 2013-12-18 | 三洋化成工業株式会社 | Dispersant for ceramic extrusion |
| JP5095377B2 (en) * | 2007-12-14 | 2012-12-12 | 積水化学工業株式会社 | Binder resin for inorganic fine particle dispersed paste composition, inorganic fine particle dispersed paste composition, inorganic fine particle dispersed paste composition for forming green sheet, and green sheet |
| CN102958591B (en) * | 2010-04-26 | 2015-08-05 | 路博润高级材料公司 | Dispersant composition |
| JP2013193912A (en) * | 2012-03-19 | 2013-09-30 | Kao Corp | Slurry composition for molding ceramic sheet |
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2014
- 2014-09-17 CN CN201480049250.2A patent/CN105517698A/en active Pending
- 2014-09-17 JP JP2015501978A patent/JPWO2015041226A1/en active Pending
- 2014-09-17 WO PCT/JP2014/074492 patent/WO2015041226A1/en active Application Filing
- 2014-09-17 KR KR1020167009250A patent/KR20160054563A/en not_active Application Discontinuation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1205619C (en) * | 1999-10-20 | 2005-06-08 | 株式会社村田制作所 | Ceramic paste composition and method of making ceramic blank sheet and multilayer electron element |
| US20090258975A1 (en) * | 2006-03-15 | 2009-10-15 | Kao Corporation | Nonaqueous pigment dispersion composition |
| CN102131574A (en) * | 2008-08-27 | 2011-07-20 | 花王株式会社 | High-molecular dispersant for inorganic pigments |
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| TW201513930A (en) | 2015-04-16 |
| JPWO2015041226A1 (en) | 2017-03-02 |
| WO2015041226A1 (en) | 2015-03-26 |
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