TWI432397B - Ceramic manufacturing and laminated ceramic electronic parts manufacturing method - Google Patents
Ceramic manufacturing and laminated ceramic electronic parts manufacturing method Download PDFInfo
- Publication number
- TWI432397B TWI432397B TW98128253A TW98128253A TWI432397B TW I432397 B TWI432397 B TW I432397B TW 98128253 A TW98128253 A TW 98128253A TW 98128253 A TW98128253 A TW 98128253A TW I432397 B TWI432397 B TW I432397B
- Authority
- TW
- Taiwan
- Prior art keywords
- ceramic
- structural unit
- weight
- laminated
- ceramic green
- Prior art date
Links
- 239000000919 ceramic Substances 0.000 title claims description 284
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000002245 particle Substances 0.000 claims description 81
- 239000002270 dispersing agent Substances 0.000 claims description 78
- 239000000843 powder Substances 0.000 claims description 52
- 229920000642 polymer Polymers 0.000 claims description 44
- 239000002994 raw material Substances 0.000 claims description 37
- 239000002002 slurry Substances 0.000 claims description 37
- 239000011230 binding agent Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 239000004020 conductor Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims 2
- 238000000576 coating method Methods 0.000 claims 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 21
- 229910002113 barium titanate Inorganic materials 0.000 description 21
- 239000003985 ceramic capacitor Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000178 monomer Substances 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- 230000003746 surface roughness Effects 0.000 description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- -1 2-ethoxyethyl Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000004931 aggregating effect Effects 0.000 description 2
- 125000002511 behenyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000000717 retained effect Effects 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
- 238000003756 stirring Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101001062854 Rattus norvegicus Fatty acid-binding protein 5 Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000007869 azo polymerization initiator Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 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 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 210000001654 germ layer Anatomy 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- GYNCSAXAHWFRMX-UHFFFAOYSA-N n-(2-methoxyethyl)-n-methylprop-2-enamide Chemical compound COCCN(C)C(=O)C=C GYNCSAXAHWFRMX-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/6344—Copolymers containing at least three different monomers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
- C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
- C04B35/6263—Wet mixtures characterised by their solids loadings, i.e. the percentage of solids
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63424—Polyacrylates; Polymethacrylates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63444—Nitrogen-containing polymers, e.g. polyacrylamides, polyacrylonitriles, polyvinylpyrrolidone [PVP], polyethylenimine [PEI]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5409—Particle size related information expressed by specific surface values
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5463—Particle size distributions
- C04B2235/5481—Monomodal
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6025—Tape casting, e.g. with a doctor blade
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/963—Surface properties, e.g. surface roughness
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Ceramic Capacitors (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Description
本發明係關於一種陶瓷成形體及積層型陶瓷電子零件之製造方法，尤其是關於可較好地用以形成積層型陶瓷電子零件中的陶瓷層之陶瓷成形體、及使用其而實施之積層型陶瓷電子零件之製造方法。The present invention relates to a method for producing a ceramic molded body and a laminated ceramic electronic component, and more particularly to a ceramic molded body which can be preferably used for forming a ceramic layer in a laminated ceramic electronic component, and a laminated type which is used therewith Manufacturing method of ceramic electronic parts.
以積層陶瓷電容器為代表之積層型陶瓷電子零件包含陶瓷積層體，該陶瓷積層體具有複數層陶瓷層與複數個內部電極交替積層之結構。為了形成陶瓷層而準備陶瓷漿料，要獲得陶瓷積層體時，係採用以下方法：預先製作藉由將陶瓷漿料成形為片狀而獲得之陶瓷生片，然後將該等複數片陶瓷生片堆疊；或者反覆地印刷、乾燥陶瓷漿料。A laminated ceramic electronic component typified by a multilayer ceramic capacitor includes a ceramic laminate having a structure in which a plurality of ceramic layers and a plurality of internal electrodes are alternately laminated. In order to form a ceramic layer to prepare a ceramic slurry, in order to obtain a ceramic laminate, the following method is employed: a ceramic green sheet obtained by forming a ceramic slurry into a sheet shape is prepared in advance, and then the plurality of ceramic green sheets are formed. Stacking; or printing and drying the ceramic slurry repeatedly.
對於此處所用之陶瓷漿料而言，重要的是使陶瓷原料粉末與黏合劑成分均勻地分散於溶劑中，因此，陶瓷漿料中添加有不飽和脂肪酸等分散劑，其吸附於陶瓷原料粉末之表面，用以提高分散性(例如，參照專利文獻1)。For the ceramic slurry used herein, it is important that the ceramic raw material powder and the binder component are uniformly dispersed in the solvent. Therefore, a dispersant such as an unsaturated fatty acid is added to the ceramic slurry, and the ceramic raw material powder is adsorbed to the ceramic raw material powder. The surface is used to improve the dispersibility (for example, refer to Patent Document 1).
近年來，如積層陶瓷電容器為了增大電容般，為了提高積層型陶瓷電子零件之特性，而要求使積層型陶瓷電子零件所包含之陶瓷層薄層化，藉此增加積層片數。為了應對該薄層化之要求，需要使陶瓷層中所含之陶瓷原料粉末微粒化，使其粒徑達到例如100nm以下。In recent years, in order to increase the capacitance of a multilayer ceramic capacitor, in order to increase the capacitance of the multilayer ceramic electronic component, it is required to thin the ceramic layer included in the laminated ceramic electronic component, thereby increasing the number of laminated layers. In order to cope with the demand for the thinning, it is necessary to atomize the ceramic raw material powder contained in the ceramic layer to have a particle diameter of, for example, 100 nm or less.
但是，陶瓷原料粉末越微粒化，則陶瓷漿料中陶瓷原料粉末彼此越容易凝集，故而陶瓷原料粉末之分散性惡化。如此般，若一面使用含有分散性惡化之陶瓷原料粉末之陶瓷漿料形成陶瓷層，一面製作陶瓷積層體，則有時各陶瓷層之密度下降、或表面粗糙度惡化，導致所得之積層型陶瓷電子零件發生短路不良或絕緣不良等故障。However, as the ceramic raw material powder becomes finer, the ceramic raw material powders in the ceramic slurry are more likely to aggregate, and the dispersibility of the ceramic raw material powder is deteriorated. When a ceramic layer is formed by using a ceramic slurry containing a ceramic raw material powder having poor dispersibility, the density of each ceramic layer is lowered or the surface roughness is deteriorated, resulting in the resulting laminated ceramic. A malfunction of a short-circuit or poor insulation of an electronic component.
再者，為了防止陶瓷原料粉末彼此凝集，亦可考慮增多上述分散劑之添加量，但若如此般過量添加分散劑，則雖然可某種程度地抑制陶瓷原料粉末彼此凝集，但不僅會使陶瓷生片等陶瓷成形體中之陶瓷原料粉末的填充密度下降，而且由黏合劑成分所帶來之陶瓷原料粉末間之結合力亦降低，其結果，陶瓷成形體之強度下降。Further, in order to prevent the ceramic raw material powders from aggregating with each other, it is also conceivable to increase the amount of the dispersant added. However, if the dispersant is excessively added in this manner, the ceramic raw material powders can be inhibited from agglomerating to some extent, but not only ceramics but also ceramics. The filling density of the ceramic raw material powder in the ceramic molded body such as the green sheet is lowered, and the bonding strength between the ceramic raw material powders due to the binder component is also lowered, and as a result, the strength of the ceramic formed body is lowered.
[專利文獻1]日本專利特公平7-108817號公報[Patent Document 1] Japanese Patent Special Fair 7-108817
因此，本發明之目的在於提供一種陶瓷成形體，其可解決如上所述之由於陶瓷原料粉末彼此凝集而引起之問題。Accordingly, it is an object of the present invention to provide a ceramic formed body which solves the problems caused by the aggregation of ceramic raw material powders with each other as described above.
本發明之其他目的在於提供一種積層型陶瓷電子零件之製造方法，其係使用上述之陶瓷成形體而實施者。Another object of the present invention is to provide a method for producing a laminated ceramic electronic component which is carried out by using the above-described ceramic molded body.
本發明首先係針對於一種陶瓷成形體，其係藉由對包含陶瓷原料粉末、黏合劑成分及溶劑之陶瓷漿料賦予特定之形狀而獲得者。為了解決上述技術性課題，構成陶瓷原料粉末之陶瓷粒子之表面係由分散劑所覆蓋，且該分散劑係包含含有下述共聚物之高分子分散劑者，上述共聚物係包含：全部結構單元中之5~45重量%的以下述通式(1)所示之結構單元A；全部結構單元中之50~90重量%的以下述通式(2)所示之結構單元B；及以相對於結構單元B之重量比(結構單元C/結構單元B)計為0.05~0.7的以下述通式(3)所示之結構單元C。The present invention is first directed to a ceramic formed body obtained by imparting a specific shape to a ceramic slurry containing a ceramic raw material powder, a binder component, and a solvent. In order to solve the above-described technical problems, the surface of the ceramic particles constituting the ceramic raw material powder is covered with a dispersing agent, and the dispersing agent contains a polymer dispersing agent containing a copolymer containing all structural units. 5 to 45% by weight of the structural unit A represented by the following general formula (1); 50 to 90% by weight of all structural units of the structural unit B represented by the following general formula (2); The weight ratio of the structural unit B (structural unit C/structural unit B) is 0.05 to 0.7 of the structural unit C represented by the following general formula (3).
於上述式(1)及(2)中，R1 、R2 、R3 、R4 、R5 及R6 相同或不同，表示氫原子或碳數為1~2之烷基，R7 表示碳數為1~4之直鏈或支鏈之伸烷基，R8 表示氫原子或碳數為1~2之烷基，X1 表示氧原子或NH，M表示氫原子或陽離子，n表示1~50之數。In the above formulae (1) and (2), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R 7 represents a straight or branched alkyl group having a carbon number of 1 to 4, R 8 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, X 1 represents an oxygen atom or NH, M represents a hydrogen atom or a cation, and n represents 1~50 number.
於上述式(3)中，R9 、R10 及R11 相同或不同，表示氫原子或碳數為1~2之烷基，X2 表示氧原子或NH，R12 及R13 表示碳數為1~30之直鏈、支鏈或環狀之烷基或者烯基、或芳基。In the above formula (3), R 9 , R 10 and R 11 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, X 2 represents an oxygen atom or NH, and R 12 and R 13 represent a carbon number. It is a linear, branched or cyclic alkyl or alkenyl group or an aryl group of 1 to 30.
對於本發明之陶瓷成形體而言，較好的是以使陶瓷粒子之直徑為10nm~300nm之方式將陶瓷粒子微粒化。如此，當陶瓷粒子之直徑在10nm~300nm之範圍時，高分子分散劑之添加量較好的是相對於陶瓷粒子100重量份為0.1~10重量份。In the ceramic formed article of the present invention, it is preferred that the ceramic particles are atomized so that the diameter of the ceramic particles is from 10 nm to 300 nm. As described above, when the diameter of the ceramic particles is in the range of 10 nm to 300 nm, the amount of the polymer dispersant to be added is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the ceramic particles.
又，本發明亦係針對於一種積層型陶瓷電子零件之製造方法，其包括以下步驟：製作未加工之陶瓷積層體，該未加工之陶瓷積層體包含積層的複數層之陶瓷生胚層、及沿陶瓷生胚層間之特定界面而形成之內部導體膜；以及焙燒未加工之陶瓷積層體。於本發明之積層型陶瓷電子零件之製造方法中，上述未加工之陶瓷積層體所包含之陶瓷生胚層之特徵在於：其包含本發明之陶瓷成形體。Moreover, the present invention is also directed to a method of manufacturing a laminated ceramic electronic component, comprising the steps of: preparing an unprocessed ceramic laminate comprising a plurality of layers of ceramic green layers, and along An inner conductor film formed by a specific interface between ceramic green sheets; and a calcined unprocessed ceramic laminate. In the method for producing a laminated ceramic electronic component according to the present invention, the ceramic green layer included in the unprocessed ceramic laminate is characterized in that it comprises the ceramic molded body of the present invention.
於本發明之積層型陶瓷電子零件之製造方法中，製作未加工之陶瓷積層體時，於第1實施形態中係實施以下步驟：製作複數片之包含形成陶瓷生胚層之陶瓷成形體的陶瓷生片，以及堆疊複數片之陶瓷生片；於第2實施形態中係實施下述步驟：藉由反覆進行塗佈構成陶瓷成形體之陶瓷漿料之步驟，而形成積層的複數層之陶瓷生胚層。In the method for producing a laminated ceramic electronic component according to the present invention, in the case of producing an unprocessed ceramic laminate, in the first embodiment, the following steps are carried out: a ceramic sheet containing a ceramic formed body in which a ceramic green layer is formed is produced in a plurality of sheets. a sheet, and a ceramic green sheet in which a plurality of sheets are stacked; in the second embodiment, the step of applying a ceramic slurry constituting the ceramic formed body to form a laminated plurality of layers of the ceramic green layer is carried out. .
根據本發明，藉由使用如上所述之高分子分散劑，可以適度的添加量而利用分散劑均勻且高效率地覆蓋陶瓷原料粉末之表面，故而即便使用易於凝集的微粒之陶瓷原料粉末，亦可抑制凝集，形成高填充率之陶瓷成形體。According to the present invention, by using the polymer dispersant as described above, the surface of the ceramic raw material powder can be uniformly and efficiently coated with a dispersing agent in an appropriate amount, so that even if a ceramic raw material powder which is easy to aggregate is used, Aggregation can be suppressed to form a ceramic molded body having a high filling rate.
因此，若使用構成此種陶瓷成形體之陶瓷漿料來製作積層型陶瓷電子零件，則可大幅降低短路不良或絕緣不良等的不良發生率。Therefore, when a ceramic ceramic component constituting such a ceramic molded body is used to produce a laminated ceramic electronic component, the occurrence rate of defects such as short-circuit failure or insulation failure can be greatly reduced.
如上所述，本發明之陶瓷成形體含有陶瓷原料粉末、黏合劑成分及溶劑。對陶瓷原料粉末之集合體賦予特定之形狀，且該對陶瓷原料粉末之集合體賦予的特定之形狀藉由黏合劑而得到維持。As described above, the ceramic formed body of the present invention contains the ceramic raw material powder, the binder component, and the solvent. The aggregate of the ceramic raw material powders is given a specific shape, and the specific shape imparted by the aggregate of the ceramic raw material powders is maintained by the binder.
為了防止陶瓷原料粉末彼此凝集，藉由分散劑而覆蓋構成陶瓷原料粉末之陶瓷粒子之表面。該分散劑包含含有下述共聚物之高分子分散劑，上述共聚物係包含：全部結構單元中之5~45重量%的以下述通式(1)所示之結構單元A；全部結構單元中之50~90重量%的以下述通式(2)所示之結構單元B；及以相對於結構單元B之重量比(結構單元C/結構單元B)計為0.05~0.7的以下述通式(3)所示之結構單元C。In order to prevent the ceramic raw material powders from aggregating with each other, the surface of the ceramic particles constituting the ceramic raw material powder is covered with a dispersing agent. The dispersant comprises a polymer dispersant containing a copolymer comprising 5 to 45% by weight of all structural units of the structural unit A represented by the following formula (1); 50 to 90% by weight of the structural unit B represented by the following formula (2); and a weight ratio of the structural unit B (structural unit C / structural unit B) of 0.05 to 0.7 (3) The structural unit C shown.
於上述式(1)及(2)中，R1 、R2 、R3 、R4 、R5 及R6 相同或不同，表示氫原子或碳數為1~2之烷基，R7 表示碳數為1~4之直鏈或支鏈之伸烷基，R8 表示氫原子或碳數為1~2之烷基，X1 表示氧原子或NH，M表示氫原子或陽離子，n表示1~50之數。In the above formulae (1) and (2), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R 7 represents a straight or branched alkyl group having a carbon number of 1 to 4, R 8 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, X 1 represents an oxygen atom or NH, M represents a hydrogen atom or a cation, and n represents 1~50 number.
於上述式(3)中，R9 、R10 及R11 相同或不同，表示氫原子或碳數為1~2之烷基，X2 表示氧原子或NH，R12 及R13 表示碳數為1~30之直鏈、支鏈或環狀之烷基或者烯基、或芳基。In the above formula (3), R 9 , R 10 and R 11 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, X 2 represents an oxygen atom or NH, and R 12 and R 13 represent a carbon number. It is a linear, branched or cyclic alkyl or alkenyl group or an aryl group of 1 to 30.
該高分子分散劑例如可利用下述等公知之方法而獲得，亦即利用溶液聚合法使包含以下單體的單體成分聚合：成為上述結構單元A的具有羧基等可中和之酸性基之酸性單體、或可於聚合後加成可中和之酸性基之單體；成為上述結構單元B的非離子性單體、或可於聚合後導入非離子性基之單體；以及成為上述結構單元C之疏水性單體。The polymer dispersant can be obtained, for example, by a known method such as polymerization of a monomer component containing the following monomer by a solution polymerization method: a neutralizable acidic group having a carboxyl group or the like as the structural unit A. An acidic monomer or a monomer capable of adding a neutralizable acidic group after polymerization; a nonionic monomer which is the above structural unit B, or a monomer which can introduce a nonionic group after polymerization; A hydrophobic monomer of structural unit C.
作為成為上述構成單位結構單元A之酸性單體，例如可舉出：(甲基)丙烯酸、丁烯酸等。Examples of the acidic monomer to be the unit structural unit A to be formed include (meth)acrylic acid and crotonic acid.
作為成為上述結構單元B之非離子性單體，例如可舉出：甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚(乙二醇/丙二醇)單(甲基)丙烯酸酯、乙氧基聚(乙二醇/丙二醇)單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、2-甲氧基乙基(甲基)丙烯醯胺、2-乙氧基乙基(甲基)丙烯醯胺、3-甲氧基丙基(甲基)丙烯醯胺等。Examples of the nonionic monomer to be the structural unit B include methoxypolyethylene glycol (meth) acrylate and methoxy poly(ethylene glycol/propylene glycol) mono(meth) acrylate. Ethoxy poly(ethylene glycol/propylene glycol) mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-methoxyethyl ( Methyl) acrylamide, 2-ethoxyethyl (meth) acrylamide, 3-methoxypropyl (meth) acrylamide, and the like.
作為成為上述結構單元C之疏水性單體，例如可舉出：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸山萮基酯等之酯化合物；丁基(甲基)丙烯醯胺、辛基(甲基)丙烯醯胺、月桂基(甲基)丙烯醯胺、硬脂基(甲基)丙烯醯胺、山萮基(甲基)丙烯醯胺等之醯胺化合物；1-癸烯、1-十八烯等之α-烯烴；以及苯乙烯等。Examples of the hydrophobic monomer to be the structural unit C include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and octyl (meth)acrylate. Esters of methyl lauryl methacrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, etc.; butyl (meth) acrylamide, octyl (meth) acrylamide , a decylamine compound such as lauryl (meth) acrylamide, stearyl (meth) acrylamide, behenyl (meth) acrylamide, etc.; 1-decene, 1-octadecene, etc. Α-olefin; and styrene and the like.
作為溶液聚合中所使用之溶劑，例如可使用：芳香族烴(甲苯、二甲苯等)、低級醇(乙醇、異丙醇等)、酮(丙酮、甲基乙基酮)、四氫呋喃、二乙二醇、二甲醚等之有機溶劑。溶劑量較好的是以重量比計為單體總量之0.5~10倍。As the solvent to be used in the solution polymerization, for example, an aromatic hydrocarbon (such as toluene or xylene), a lower alcohol (ethanol, isopropanol, etc.), a ketone (acetone, methyl ethyl ketone), tetrahydrofuran, or diethyl ether can be used. An organic solvent such as a diol or a dimethyl ether. The amount of the solvent is preferably from 0.5 to 10 times the total amount of the monomers by weight.
作為聚合起始劑，可使用公知之自由基聚合起始劑，例如可舉出：偶氮系聚合起始劑、過氧化氫類、過氧化二烷基類、過氧化二醯基類、過氧化酮類等。聚合起始劑量較好的是相對於單體成分總量為0.01~5莫耳%，更好的是0.01~3莫耳%，最好的是0.01~1莫耳%。聚合反應較好的是在氮氣流下、於60~180℃之溫度範圍內進行，反應時間較好的是0.5~20小時。As the polymerization initiator, a known radical polymerization initiator can be used, and examples thereof include an azo polymerization initiator, hydrogen peroxide, a dialkyl peroxide, and a dioxonium peroxide. Oxide ketones, etc. The polymerization starting dose is preferably from 0.01 to 5 mol%, more preferably from 0.01 to 3 mol%, most preferably from 0.01 to 1 mol%, based on the total amount of the monomer components. The polymerization reaction is preferably carried out in a temperature range of 60 to 180 ° C under a nitrogen stream, and the reaction time is preferably 0.5 to 20 hours.
高分子分散劑中，結構單元A、結構單元B及結構單元C之排列可為無規、嵌段及接枝中之任一種。又，若為滿足上述全部含量範圍者，則亦可包含該等結構單元A~C以外之結構單元。In the polymer dispersant, the arrangement of the structural unit A, the structural unit B, and the structural unit C may be any of random, block, and graft. Further, if all of the above content ranges are satisfied, structural units other than the structural units A to C may be included.
對於高分子分散劑之重量平均分子量，就陶瓷原料粉末之分散性之觀點考慮，較好的是15000~200000，更好的是20000~100000。其中，於陶瓷原料粉末之平均粒徑為未達100nm的較小粒徑之情形時，高分子分散劑之重量平均分子量較好的是1000~未達15000，更好的是2000~10000。再者，該重量平均分子量係藉由GPC(Gel Permeation Chromatography，凝膠滲透層析法)而測定之值。The weight average molecular weight of the polymer dispersant is preferably from 15,000 to 200,000, more preferably from 20,000 to 100,000, from the viewpoint of dispersibility of the ceramic raw material powder. In the case where the average particle diameter of the ceramic raw material powder is a small particle diameter of less than 100 nm, the weight average molecular weight of the polymer dispersant is preferably from 1,000 to less than 15,000, more preferably from 2,000 to 10,000. Further, the weight average molecular weight is a value measured by GPC (Gel Permeation Chromatography).
一般認為，於非水系漿料中，係藉由陶瓷粒子表面之鹼性部位與分散劑之酸性部位之相互作用，而使分散劑吸附於陶瓷粒子表面。吸附於陶瓷粒子表面之分散劑形成立體障壁，抑制陶瓷粒子彼此凝集。It is considered that in the non-aqueous slurry, the dispersant is adsorbed on the surface of the ceramic particles by the interaction between the basic portion of the surface of the ceramic particles and the acidic portion of the dispersant. The dispersing agent adsorbed on the surface of the ceramic particles forms a three-dimensional barrier and suppresses aggregation of the ceramic particles.
於上述專利文獻1所揭示之技術中，要使分散劑吸附於陶瓷粒子表面之整個面時，由於吸附效率較差，且所吸附之分散劑之保持能力較低，故而例如當陶瓷粒子之表面係由表現鹼性之材料所形成時，即便加以調整使得陶瓷粒子表面之總鹼量與分散劑之總酸量達到等量，亦會相對較多地殘留未吸附於陶瓷粒子表面之分散劑。In the technique disclosed in the above Patent Document 1, when the dispersing agent is adsorbed on the entire surface of the surface of the ceramic particles, the adsorption efficiency is poor, and the ability of the adsorbed dispersing agent to be held is low, for example, when the surface of the ceramic particles is When formed of a material exhibiting alkalinity, even if the total alkali amount on the surface of the ceramic particles is equal to the total amount of the acid of the dispersing agent, the dispersing agent which is not adsorbed on the surface of the ceramic particles remains relatively much.
又，所吸附之分散劑有時亦會由於其結構而使得立體障壁無法充分發揮功能，導致抑制陶瓷粒子彼此凝集之效果不充分。Further, the adsorbent to be adsorbed may not sufficiently function as a three-dimensional barrier due to its structure, and the effect of suppressing aggregation of ceramic particles may be insufficient.
若存在表面未吸附有分散劑之陶瓷粒子，且所吸附之分散劑之立體障壁無法充分發揮功能，則會以此為起點而引起陶瓷粒子彼此凝集，陶瓷漿料之分散性惡化。如上所述之不良狀況尤其在陶瓷粒子之粒徑微粒化為例如100nm以下時變得顯著。When the ceramic particles having no dispersant adsorbed on the surface are present and the three-dimensional barrier of the adsorbed dispersant does not sufficiently function, the ceramic particles are aggregated as a starting point, and the dispersibility of the ceramic slurry is deteriorated. The defect as described above becomes remarkable particularly when the particle diameter of the ceramic particles is, for example, 100 nm or less.
相對於此，根據本發明之陶瓷成形體，其中所含之高分子分散劑對陶瓷粒子表面之吸附率較高，且所吸附之分散劑之保持能力較高，進而作為立體障壁之功能較高。因此，無需過量地添加此種高分子分散劑，可藉由必要之最低限度之分散劑量，而獲得分散劑吸附於陶瓷粒子表面形成立體障壁之狀態。因此，即便陶瓷粒子之粒徑微粒化為例如100nm以下，亦可抑制陶瓷漿料中之陶瓷原料粉末之凝集，獲得處於陶瓷原料粉末均勻地分散之狀態下之陶瓷成形體。On the other hand, according to the ceramic formed article of the present invention, the polymer dispersant contained therein has a high adsorption rate on the surface of the ceramic particles, and the retained dispersant has a high retention ability, and thus has a higher function as a three-dimensional barrier. . Therefore, it is not necessary to excessively add such a polymer dispersant, and a state in which the dispersant is adsorbed on the surface of the ceramic particles to form a three-dimensional barrier can be obtained by a minimum necessary dispersion amount. Therefore, even if the particle diameter of the ceramic particles is atomized to, for example, 100 nm or less, the aggregation of the ceramic raw material powder in the ceramic slurry can be suppressed, and the ceramic molded body in a state in which the ceramic raw material powder is uniformly dispersed can be obtained.
其結果，可提高陶瓷成形體中之陶瓷原料粉末之填充密度，從而可提高陶瓷成形體之密度。又，由於可降低分散劑在陶瓷成形體中所佔之比例，故而可增加陶瓷成形體之強度。As a result, the packing density of the ceramic raw material powder in the ceramic formed body can be increased, and the density of the ceramic formed body can be increased. Further, since the proportion of the dispersant in the ceramic formed body can be reduced, the strength of the ceramic formed body can be increased.
又，由於本發明中所使用之高分子分散劑之吸附效率較高，故而可於短時間內完成分散處理。因此，可提高生產性，並且可謀求減少分散處理中陶瓷原料粉末所受到之損害。因此，可維持陶瓷原料粉末本來所具有之結晶性而提供陶瓷成形體。Further, since the polymer dispersant used in the present invention has a high adsorption efficiency, the dispersion treatment can be completed in a short time. Therefore, productivity can be improved, and damage to the ceramic raw material powder in the dispersion treatment can be reduced. Therefore, the ceramic molded body can be provided by maintaining the crystallinity inherent to the ceramic raw material powder.
本發明之陶瓷成形體之一實施形態係製造積層型陶瓷電子零件時所準備之陶瓷生片。An embodiment of the ceramic molded body of the present invention is a ceramic green sheet prepared when a laminated ceramic electronic component is produced.
圖1係表示作為利用本發明之製造方法而製造的積層型陶瓷電子零件之一例之積層陶瓷電容器1的剖面圖。Fig. 1 is a cross-sectional view showing a multilayer ceramic capacitor 1 as an example of a laminated ceramic electronic component manufactured by the manufacturing method of the present invention.
積層陶瓷電容器1包括陶瓷積層體5，該陶瓷積層體5係包含下述者而構成：積層之複數層之陶瓷層2、與沿陶瓷層2間之特定界面而形成的複數層之內部導體膜3及4。The multilayer ceramic capacitor 1 includes a ceramic laminate 5 comprising a ceramic layer 2 of a plurality of layers laminated, and a plurality of inner conductor films formed at a specific interface between the ceramic layers 2. 3 and 4.
於陶瓷積層體5之外表面上的相互不同的位置上，形成有第1及第2外部端子電極6及7。於圖1所示之積層陶瓷電容器1中，第1及第2外部端子電極6及7形成於陶瓷積層體5之相互對向之各端面上。內部導體膜3及4有與第1外部端子電極6電性連接之第1內部導體膜3、以及與第2外部端子電極7電性連接之第2內部導體膜4，該等第1及第2內部導體膜3及4在積層方向上交替配置。The first and second external terminal electrodes 6 and 7 are formed at mutually different positions on the outer surface of the ceramic laminate 5 . In the multilayer ceramic capacitor 1 shown in FIG. 1, the first and second external terminal electrodes 6 and 7 are formed on the respective end faces of the ceramic laminate 5 opposite to each other. The inner conductor films 3 and 4 have a first inner conductor film 3 electrically connected to the first outer terminal electrode 6 and a second inner conductor film 4 electrically connected to the second outer terminal electrode 7, and the first and the first 2 The inner conductor films 3 and 4 are alternately arranged in the lamination direction.
為了製造上述積層陶瓷電容器1，而製作陶瓷積層體5之未加工狀態者。未加工之陶瓷積層體包含應成為陶瓷層2之積層的複數層之陶瓷生胚層，且沿陶瓷生胚層間之特定界面而形成有內部導體膜3及4。繼而，藉由焙燒未加工之陶瓷積層體，而獲得燒結之陶瓷積層體5，其後形成外部端子電極6及7，藉此完成積層陶瓷電容器1。In order to manufacture the above-mentioned multilayer ceramic capacitor 1, the unprocessed state of the ceramic laminate 5 is produced. The unprocessed ceramic laminate includes a plurality of layers of ceramic green sheets which should be laminated layers of the ceramic layers 2, and inner conductor films 3 and 4 are formed along specific interfaces between the ceramic green sheets. Then, the sintered ceramic laminate 5 is obtained by firing the unprocessed ceramic laminate, and thereafter the external terminal electrodes 6 and 7 are formed, whereby the laminated ceramic capacitor 1 is completed.
於上述未加工之陶瓷積層體中，陶瓷生胚層係藉由本發明之陶瓷成形體而形成。更具體而言，為了製作未加工之陶瓷積層體，而準備包含陶瓷原料粉末、黏合劑成分及溶劑之陶瓷漿料，將該陶瓷漿料成形為片狀，藉此製作複數片之形成陶瓷生胚層之陶瓷生片。於特定的陶瓷生片上，藉由例如印刷導電膏而形成內部導體膜3及4。然後，堆疊該等複數片之陶瓷生片。In the above unprocessed ceramic laminate, the ceramic green layer is formed by the ceramic formed body of the present invention. More specifically, in order to produce an unprocessed ceramic laminate, a ceramic slurry containing a ceramic raw material powder, a binder component, and a solvent is prepared, and the ceramic slurry is formed into a sheet shape, thereby producing a plurality of ceramic sheets. Ceramic green sheets of germ layers. The inner conductor films 3 and 4 are formed on a specific ceramic green sheet by, for example, printing a conductive paste. Then, the plurality of ceramic green sheets are stacked.
上述陶瓷生片中之陶瓷粒子之填充密度受上一階段之陶瓷漿料之分散性的影響，若無法實現充分的分散條件，則陶瓷生片中之陶瓷粒子之填充密度將下降。因此，亦可考慮過量地添加分散劑等，來促進分散劑向陶瓷粒子表面吸附，但此時分散劑在陶瓷生片中所佔之比率增高，其結果導致陶瓷生片中之陶瓷填充率下降。The packing density of the ceramic particles in the above ceramic green sheets is affected by the dispersibility of the ceramic slurry in the previous stage, and if sufficient dispersion conditions are not achieved, the packing density of the ceramic particles in the ceramic green sheets is lowered. Therefore, it is also conceivable to excessively add a dispersant or the like to promote the adsorption of the dispersant to the surface of the ceramic particles, but at this time, the ratio of the dispersant in the ceramic green sheets is increased, and as a result, the ceramic filling rate in the ceramic green sheets is lowered. .
又，於陶瓷生片中，通常係分子量較大之黏合劑成分夾雜於陶瓷粒子之間，以黏合劑成分自身之凝集力來保持其強度，但若分散劑在陶瓷生片中所佔之比率增高，則陶瓷生片本身之強度下降，容易在印刷步驟或積層步驟等後續步驟中受到損害，從而引起品質不良。Further, in the ceramic green sheet, a binder component having a relatively large molecular weight is usually interposed between the ceramic particles, and the strength of the binder component itself is maintained by the cohesive force of the binder component, but the ratio of the dispersant in the ceramic green sheet is When the height is increased, the strength of the ceramic green sheet itself is lowered, and it is easily damaged in subsequent steps such as a printing step or a lamination step, resulting in poor quality.
根據藉由本發明之陶瓷成形體而形成之陶瓷生片，如上所述，其中所含之高分子分散劑對陶瓷粒子表面之吸附率較高，且所吸附之分散劑之保持能力較高，進而作為立體障壁之功能較高，故而可提高陶瓷生片中之陶瓷原料粉末之填充密度，從而可提高陶瓷生片之密度。又，由於可降低分散劑在陶瓷生片中所佔之比例，故而可增加陶瓷生片之強度，從而可減小於印刷步驟或積層步驟等後續步驟中所受損害之影響。又，由於可抑制陶瓷原料粉末凝集，故而可使陶瓷生片之表面平滑。According to the ceramic green sheet formed by the ceramic formed body of the present invention, as described above, the polymer dispersant contained therein has a high adsorption rate on the surface of the ceramic particles, and the retained dispersant has a high retention ability, and further Since the function as a three-dimensional barrier is high, the packing density of the ceramic raw material powder in the ceramic green sheet can be increased, and the density of the ceramic green sheet can be increased. Further, since the proportion of the dispersant in the ceramic green sheet can be reduced, the strength of the ceramic green sheet can be increased, so that the influence of damage in subsequent steps such as the printing step or the lamination step can be reduced. Further, since the ceramic raw material powder can be suppressed from agglomerating, the surface of the ceramic green sheet can be made smooth.
因此，若使用此種陶瓷生片來製作陶瓷積層體，則於所得之積層型陶瓷電子零件中，可大幅降低短路不良或絕緣不良等之不良發生率。Therefore, when such a ceramic green sheet is used to produce a ceramic laminate, the resulting laminated ceramic electronic component can greatly reduce the occurrence rate of defects such as short-circuit failure or insulation failure.
又，如上所述可在短時間內完成分散處理，故而可維持陶瓷原料粉末本來所具有之結晶性而將陶瓷原料粉末生片化。因此，於積層型陶瓷電子零件中，可穩定地獲得與設計一致之特性。Further, since the dispersion treatment can be completed in a short time as described above, the ceramic raw material powder can be grown by maintaining the crystallinity inherent to the ceramic raw material powder. Therefore, in the laminated ceramic electronic component, the characteristics consistent with the design can be stably obtained.
再者，如上所述般陶瓷成形體為陶瓷生片時所發揮之效果，在製造積層陶瓷電子零件時所製作的未加工之陶瓷積層體所包含的複數層陶瓷生胚層係藉由反覆進行塗佈陶瓷漿料之步驟而形成時亦同樣可發揮出。Further, as described above, when the ceramic formed body is a ceramic green sheet, the plurality of layers of the ceramic green layer contained in the unprocessed ceramic laminate produced in the production of the laminated ceramic electronic component are repeatedly coated. The same can be exhibited when the step of laying the ceramic slurry is formed.
一般而言，當進行微粒化使陶瓷成形體中所含之陶瓷粒子之直徑為10nm~300nm時，凝集力尤其增加，變得難以使陶瓷粒子均勻地分散於分散介質中。因此，要獲得均勻分散之陶瓷漿料較為困難，難以成形出厚度為10μm以下之缺陷較少之陶瓷生片。In general, when the diameter of the ceramic particles contained in the ceramic formed body is from 10 nm to 300 nm, the cohesive force is particularly increased, and it becomes difficult to uniformly disperse the ceramic particles in the dispersion medium. Therefore, it is difficult to obtain a ceramic slurry which is uniformly dispersed, and it is difficult to form a ceramic green sheet having a defect having a thickness of 10 μm or less.
相對於此，於本發明之陶瓷成形體中，即便陶瓷粒子之直徑微粒化為10nm~300nm，亦可使其均勻地分散，即便厚度為3μm以下，亦可成形出缺陷較少之陶瓷生片。因此，若應用於如圖1所示之積層陶瓷電容器1中，則可推進陶瓷層2進一步薄層化，從而可獲得較大電容。On the other hand, in the ceramic molded body of the present invention, even if the diameter of the ceramic particles is 10 nm to 300 nm, the ceramic particles can be uniformly dispersed, and even if the thickness is 3 μm or less, ceramic green sheets having less defects can be formed. . Therefore, if applied to the multilayer ceramic capacitor 1 shown in Fig. 1, the ceramic layer 2 can be further thinned, so that a large capacitance can be obtained.
如上所述，在陶瓷成形體中，於陶瓷粒子之直徑微粒化為10nm~300nm時，高分子分散劑之添加量相對於100重量份之陶瓷粒子較好的是0.1~10重量份。As described above, in the ceramic formed body, when the diameter of the ceramic particles is 10 nm to 300 nm, the amount of the polymer dispersant added is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the ceramic particles.
再者，本發明之陶瓷成形體除了上述的陶瓷生片或未加工之陶瓷積層體中之陶瓷生胚層以外，亦包含：將含有硬化型黏合劑成分之陶瓷漿料填充於鑄模中，使黏合劑成分硬化，藉此而賦予有特定形狀者。Furthermore, the ceramic formed body of the present invention comprises, in addition to the ceramic green sheet in the ceramic green sheet or the unprocessed ceramic laminated body, a ceramic slurry containing a hardening type binder component, which is filled in a mold to be bonded. The agent component is hardened, whereby a specific shape is imparted.
以下，對基於本發明而實施之實驗例進行說明。Hereinafter, an experimental example carried out based on the present invention will be described.
作為高分子分散劑，係使用以如下方式而製作者。As a polymer dispersing agent, it is used as follows.
於安裝有回流管、攪拌裝置、溫度計及氮氣導入管之可分離式燒瓶中，分別投入甲基丙烯酸硬脂基酯(新中村化學公司製造，NK-ester S)2.25g、甲氧基聚乙二醇(9)甲基丙烯酸酯(新中村化學公司製造，NK-ester M-90G，氧化乙烯之平均加成莫耳數為9)10.5g、甲基丙烯酸(和光純藥工業公司製造之試劑)2.25g、以及甲苯(和光純藥工業公司製造之試劑)6.0g，進行氮氣置換，加熱至65℃。In a separable flask equipped with a reflux tube, a stirring device, a thermometer, and a nitrogen inlet tube, stearyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK-ester S), 2.25 g, methoxypolyethyl b. Glycol (9) methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK-ester M-90G, average molar addition of ethylene oxide to 9) 10.5 g, methacrylic acid (Reagents manufactured by Wako Pure Chemical Industries, Ltd.) 2.25 g and 6.0 g of toluene (reagent manufactured by Wako Pure Chemical Industries, Ltd.) were replaced with nitrogen and heated to 65 °C.
槽內達到65℃後，添加含有2,2'-偶氮雙(2,4-二甲基戊腈)(V-65B，和光純藥工業公司製造)0.45g、及甲苯2.5g之混合物。After reaching 65 ° C in the tank, a mixture containing 0.45 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65B, manufactured by Wako Pure Chemical Industries, Ltd.) and 2.5 g of toluene was added.
其後，歷時3小時滴加含有甲基丙烯酸硬脂基酯20.25g、甲氧基聚乙二醇(9)甲基丙烯酸酯94.5g、甲基丙烯酸20.25g、甲苯90g、以及V-65B 4.05g之混合液。Thereafter, 20.25 g of stearyl methacrylate, 94.5 g of methoxypolyethylene glycol (9) methacrylate, 20.25 g of methacrylic acid, 90 g of toluene, and V-65B 4.05 were added dropwise over 3 hours. a mixture of g.
於65℃下攪拌3小時後，加以冷卻。為了調整濃度而添加甲苯，獲得作為目標之高分子分散劑之甲苯溶液。該溶液之不揮發成分為39.4重量%，高分子分散劑之重量平均分子量為44200。After stirring at 65 ° C for 3 hours, it was cooled. Toluene was added to adjust the concentration, and a toluene solution as a target polymer dispersant was obtained. The nonvolatile content of the solution was 39.4% by weight, and the weight average molecular weight of the polymer dispersant was 44,200.
以如下各比例調配以下各成分：平均粒徑為0.3μm之市售之鈦酸鋇粉末100重量份、以有效成分計為0.2重量份之上述高分子分散劑(分散劑相對於鈦酸鋇粉末之表面積為1.6mg/m2 )、黏合劑(聚乙烯丁醛黏合劑)10重量份、增塑劑(鄰苯二甲酸二辛酯)2重量份、以及作為溶劑之甲苯70重量份及乙醇70重量份。The following components were blended in the following ratios: 100 parts by weight of commercially available barium titanate powder having an average particle diameter of 0.3 μm, and 0.2 parts by weight of the above-mentioned polymer dispersant (dispersant relative to barium titanate powder) a surface area of 1.6 mg/m 2 ), 10 parts by weight of a binder (polyvinyl butyral binder), 2 parts by weight of a plasticizer (dioctyl phthalate), and 70 parts by weight of toluene as a solvent and ethanol 70 parts by weight.
於上述調配物中添加直徑為1mm之氧化鋯製磨球500重量份，以後述特定之處理時間利用球磨機進行混合‧粉碎處理，獲得實施例之陶瓷生片製造用之陶瓷漿料。500 parts by weight of a zirconia-made grinding ball having a diameter of 1 mm was added to the above-mentioned preparation, and the specific treatment time described later was mixed and pulverized by a ball mill to obtain a ceramic slurry for producing a ceramic green sheet of the example.
另一方面，除了將上述高分子分散劑更換為油酸系之分散劑，及將球磨機之處理時間變更為如下述以外，藉由相同之組成及相同之操作而獲得比較例之陶瓷生片製造用之陶瓷漿料。On the other hand, in addition to changing the polymer dispersant to an oleic acid-based dispersant, and changing the processing time of the ball mill to the following, the ceramic green sheet of the comparative example was obtained by the same composition and the same operation. Used as a ceramic slurry.
上述之球磨機之處理時間係如下所述。對於上述實施例及比較例各自之陶瓷漿料，以如下方式來求出為了獲得最合適的分散狀態而需要之球磨機處理時間。亦即，每經過特定時間的球磨機處理，使用漿料粒度分布計測定粒度，求出各陶瓷漿料中之陶瓷粒子之平均粒徑(D50)。其結果示於圖2。而且，求出各陶瓷漿料中之陶瓷粒子之平均粒徑(D50)直至不再變化時之最短時間。The processing time of the above ball mill is as follows. With respect to the ceramic slurry of each of the above examples and comparative examples, the ball mill processing time required to obtain the most suitable dispersion state was obtained as follows. That is, the particle size was measured by a slurry particle size distribution meter every time a ball mill treatment was performed, and the average particle diameter (D50) of the ceramic particles in each ceramic slurry was determined. The result is shown in Fig. 2. Further, the average particle diameter (D50) of the ceramic particles in each ceramic slurry was determined until the shortest time was no longer changed.
如圖2所示，於實施例之陶瓷漿料中，陶瓷粒子之平均粒徑(D50)下降至其一次粒徑，而且自經過約5小時後起，平均粒徑(D50)顯示為固定值。As shown in FIG. 2, in the ceramic slurry of the example, the average particle diameter (D50) of the ceramic particles decreased to the primary particle diameter thereof, and the average particle diameter (D50) showed a fixed value from about 5 hours after the lapse of about 5 hours. .
另一方面，於比較例之陶瓷漿料中，經過20小時後平均粒徑(D50)亦不停止於固定值，而且並未到達至陶瓷粒子之一次粒徑。On the other hand, in the ceramic slurry of the comparative example, the average particle diameter (D50) did not stop at a fixed value after 20 hours, and did not reach the primary particle diameter of the ceramic particles.
根據上述評價結果，要獲得實施例之陶瓷漿料時，將球磨機處理時間設定為5小時，要獲得比較例之陶瓷漿料時，將球磨機處理時間設定為20小時。According to the above evaluation results, when the ceramic slurry of the example was obtained, the ball mill treatment time was set to 5 hours, and when the ceramic slurry of the comparative example was obtained, the ball mill treatment time was set to 20 hours.
繼而，對如上所述而獲得的實施例及比較例之陶瓷漿料，應用刮刀成形法而成形片材厚度為1μm、5μm及10μm之各陶瓷生片。Then, each of the ceramic green sheets of the examples and the comparative examples obtained as described above was molded into a ceramic green sheet having a sheet thickness of 1 μm, 5 μm, and 10 μm by a doctor blade forming method.
使用原子力顯微鏡來測定如此而獲得之陶瓷生片之表面粗糙度(Ra)，進而，為了對陶瓷生片之密度定量，而求出陶瓷生片之密度比(實測密度與理論密度之比)。又，測定陶瓷生片之斷裂強度。The surface roughness (Ra) of the thus obtained ceramic green sheet was measured using an atomic force microscope, and in order to quantify the density of the ceramic green sheet, the density ratio of the ceramic green sheets (the ratio of the measured density to the theoretical density) was determined. Further, the breaking strength of the ceramic green sheets was measured.
另一方面，使用上述陶瓷生片，藉由公知之方法而製作成為試樣之積層陶瓷電容器。並且，評價所得之積層陶瓷電容器之短路發生率、及電容之溫度特性。On the other hand, a multilayer ceramic capacitor to be a sample was produced by a known method using the above ceramic green sheets. Further, the short-circuit occurrence rate of the obtained multilayer ceramic capacitor and the temperature characteristics of the capacitor were evaluated.
該等之評價結果示於表1。The evaluation results of these are shown in Table 1.
由表1可知，根據實施例，則與比較例相比陶瓷生片之表面粗糙度及密度比均為良好。又，根據實施例，則與比較例相比斷裂強度亦較高。關於該斷裂強度，尤其是在片材厚度較薄之區域中實施例與比較例之間之差明顯地顯現。As is clear from Table 1, according to the examples, the surface roughness and the density ratio of the ceramic green sheets were all better than those of the comparative examples. Further, according to the examples, the breaking strength was also higher than that of the comparative examples. Regarding the breaking strength, especially in the region where the sheet thickness was thin, the difference between the examples and the comparative examples was apparent.
進而，對於積層陶瓷電容器，若根據實施例，則與比較例相比短路發生率得到改善。此處可知，於比較例中，片材厚度為10μm以下時短路發生率驟增，而於實施例中，短路發生率極低，陶瓷層之薄層化與不良率降低兩者同時實現。Further, in the multilayer ceramic capacitor, according to the embodiment, the occurrence rate of the short circuit was improved as compared with the comparative example. Here, in the comparative example, when the sheet thickness is 10 μm or less, the occurrence rate of the short circuit is rapidly increased, and in the examples, the occurrence rate of the short circuit is extremely low, and the thinning of the ceramic layer and the reduction in the defective ratio are simultaneously achieved.
又，觀察電容之溫度特性，實施例中滿足B特性(於-25~+85℃之溫度範圍內，電容變化率為±10%以內)，而比較例中僅可滿足至X5R特性(於-55~85℃之溫度範圍內，電容變化率為±15%以內)。推測其係由於在比較例中，鈦酸鋇粉末之分散效率較差，球磨機處理時間變為較長時間，故而陶瓷本身之結晶性受到損害，特性惡化。Further, observing the temperature characteristics of the capacitor, the B characteristic is satisfied in the embodiment (the capacitance change rate is within ±10% in the temperature range of -25 to +85 ° C), and in the comparative example, only the X5R characteristic can be satisfied (in - In the temperature range of 55~85 °C, the capacitance change rate is within ±15%). It is presumed that in the comparative example, the dispersion efficiency of the barium titanate powder is inferior, and the processing time of the ball mill becomes a long time, so that the crystallinity of the ceramic itself is impaired and the characteristics are deteriorated.
於實驗例2中，除了將鈦酸鋇粉末之平均粒徑微粒化為50nm，將高分子分散劑之含量變更為以有效成分計為4.0重量份(分散劑相對於鈦酸鋇粉末之表面積為1.6mg/m2 )以外，藉由與實驗例1相同之條件及相同之操作來製作實施例之陶瓷生片及積層陶瓷電容器。In Experimental Example 2, the average particle diameter of the barium titanate powder was micronized to 50 nm, and the content of the polymer dispersant was changed to 4.0 parts by weight based on the active ingredient (the surface area of the dispersant relative to the barium titanate powder was The ceramic green sheets and the laminated ceramic capacitors of the examples were produced by the same conditions and the same operation as in Experimental Example 1, except that 1.6 mg/m 2 ).
於實驗例2中，除了將上述高分子分散劑更換為油酸系之分散劑，及變更球磨機之處理時間以外，藉由相同之組成及相同之操作來製作比較例之陶瓷生片及積層陶瓷電容器。In Experimental Example 2, a ceramic green sheet and a laminated ceramic of a comparative example were produced by the same composition and the same operation except that the polymer dispersant was replaced with an oleic acid dispersant and the processing time of the ball mill was changed. Capacitor.
又，與實驗例1之情形同樣地進行評價。其結果示於表2。Moreover, the evaluation was performed in the same manner as in the case of Experimental Example 1. The results are shown in Table 2.
實驗例2中亦與實驗例1之情形同樣，根據實施例，則與比較例相比，陶瓷生片之表面粗糙度、密度比及斷裂強度，以及積層陶瓷電容器之短路發生率及電容之溫度特性獲得了更好之結果。In Experimental Example 2, as in the case of Experimental Example 1, according to the examples, the surface roughness, the density ratio, and the breaking strength of the ceramic green sheets, and the short-circuit occurrence rate of the multilayer ceramic capacitor and the temperature of the capacitor were compared with the comparative examples. Features get better results.
又，根據該實驗例2中之實施例，則與實驗例1中之實施例相比，由於陶瓷粒徑減小，故而表面粗糙度、密度比、斷裂強度、短路發生率獲得了更好之結果。Further, according to the examples in Experimental Example 2, compared with the examples in Experimental Example 1, since the ceramic particle size was reduced, the surface roughness, the density ratio, the breaking strength, and the short-circuit occurrence rate were better. result.
另一方面，實驗例2之比較例中可觀察到下述傾向：與實驗例1之比較例相比，雖然表面粗糙度提高，但密度比及斷裂強度反而惡化，短路發生率亦惡化。On the other hand, in the comparative example of the experimental example 2, the following tendency was observed: Compared with the comparative example of the experimental example 1, although the surface roughness was improved, the density ratio and the breaking strength were worse, and the short-circuit occurrence rate was also deteriorated.
以上結果表示，根據本發明，則可應對粒徑更細之陶瓷粒子。The above results show that according to the present invention, it is possible to cope with ceramic particles having a finer particle diameter.
於實驗例3中，除了將鈦酸鋇粉末之平均粒徑進一步微粒化為10nm，將高分子分散劑之含量變更為以有效成分計為4.0重量份(分散劑相對於鈦酸鋇粉末之表面積為0.4mg/m2 )以外，藉由與實驗例1相同之條件及相同之操作來製作實施例之陶瓷生片及積層陶瓷電容器。In Experimental Example 3, the average particle diameter of the barium titanate powder was further atomized to 10 nm, and the content of the polymer dispersant was changed to 4.0 parts by weight based on the active ingredient (the surface area of the dispersant relative to the barium titanate powder). The ceramic green sheets and the laminated ceramic capacitors of the examples were produced by the same conditions and the same operation as in Experimental Example 1 except that the amount was 0.4 mg/m 2 .
於實驗例3中，亦除了將上述高分子分散劑更換為油酸系之分散劑，及變更球磨機之處理時間以外，藉由相同之組成及相同之操作來製作比較例之陶瓷生片及積層陶瓷電容器。In Experimental Example 3, a ceramic green sheet and a laminate of a comparative example were produced by the same composition and the same operation except that the polymer dispersant was replaced with an oleic acid dispersant and the processing time of the ball mill was changed. ceramic capacitor.
又，與實驗例1之情形同樣地進行評價。其結果示於表3。Moreover, the evaluation was performed in the same manner as in the case of Experimental Example 1. The results are shown in Table 3.
與實驗例1之情形同樣，根據實施例，則與比較例相比，陶瓷生片之表面粗糙度、密度比及斷裂強度，以及積層陶瓷電容器之短路發生率及電容之溫度特性獲得了更好之結果。As in the case of Experimental Example 1, according to the examples, the surface roughness, the density ratio and the breaking strength of the ceramic green sheets, and the short-circuit occurrence rate of the multilayer ceramic capacitors and the temperature characteristics of the capacitors were better than those of the comparative examples. The result.
又，該實驗例3中之實施例與實驗例1中之實施例相比，亦由於陶瓷粒徑減小故而表面粗糙度、密度比、斷裂強度、及短路發生率獲得了更好之結果。Further, in the examples in Experimental Example 3, as compared with the examples in Experimental Example 1, the surface roughness, the density ratio, the breaking strength, and the occurrence rate of the short circuit were obtained as a result of the reduction in the ceramic particle diameter.
另一方面，實驗例3之比較例中可觀察到下述傾向：與實驗例1之比較例相比，雖然表面粗糙度提高，但密度比及斷裂強度反而惡化，短路發生率亦惡化。On the other hand, in the comparative example of Experimental Example 3, the following tendency was observed: Compared with the comparative example of Experimental Example 1, although the surface roughness was improved, the density ratio and the breaking strength were rather deteriorated, and the occurrence rate of the short circuit was also deteriorated.
以上結果表示，根據本發明，則可應對粒徑更細、即與實驗例2相比粒徑更細之陶瓷粒子。As described above, according to the present invention, it is possible to cope with ceramic particles having a finer particle diameter, that is, a finer particle diameter than Experimental Example 2.
於實驗例4中，除了分別使用平均粒徑為10nm、50nm及300nm之鈦酸鋇粉末，並且將高分子分散劑之添加量在以有效成分計為0.05~20重量份之範圍內進行變更以外，藉由與實驗例1相同之條件及相同之操作來製作陶瓷生片及積層陶瓷電容器。In the experimental example 4, a barium titanate powder having an average particle diameter of 10 nm, 50 nm, and 300 nm was used, and the amount of the polymer dispersant added was changed within a range of 0.05 to 20 parts by weight based on the active ingredient. A ceramic green sheet and a laminated ceramic capacitor were produced by the same conditions and the same operation as in Experimental Example 1.
又，與實驗例1之情形同樣地進行除電容之溫度特性以外之評價。其結果示於表4~表6。其中，表4表示鈦酸鋇粉末之平均粒徑為300nm之情形，表5表示鈦酸鋇粉末之平均粒徑為50nm之情形，表6表示鈦酸鋇粉末之平均粒徑為10nm之情形。Further, in the same manner as in the case of Experimental Example 1, evaluations other than the temperature characteristics of the capacitance were performed. The results are shown in Tables 4 to 6. Here, Table 4 shows the case where the average particle diameter of the barium titanate powder is 300 nm, Table 5 shows the case where the average particle diameter of the barium titanate powder is 50 nm, and Table 6 shows the case where the average particle diameter of the barium titanate powder is 10 nm.
由表4~表6可知，高分子分散劑的最合適之添加量根據陶瓷粒子之平均粒徑之不同而不同，當陶瓷粒子之平均粒徑在10nm~300nm之範圍內時，高分子分散劑之添加量較好的是在0.1~10重量份中選擇，更好的是在0.2~5重量份中選擇。It can be seen from Tables 4 to 6 that the most suitable addition amount of the polymer dispersant differs depending on the average particle diameter of the ceramic particles, and when the average particle diameter of the ceramic particles is in the range of 10 nm to 300 nm, the polymer dispersant The amount of addition is preferably selected from 0.1 to 10 parts by weight, more preferably from 0.2 to 5 parts by weight.
以上，於實驗例1~4中，作為高分子分散劑係使用以上文中所述之方式而製造之特定者，但並不限定於此，只要為如上所述般包含含有全部結構單元中之5~45重量%的以通式(1)所示之結構單元A、全部結構單元中之50~90重量%的以通式(2)所示之結構單元B、及以相對於結構單元B之重量比(結構單元C/結構單元B)計為0.05~0.7的以通式(3)所示之結構單元C的共聚物之高分子分散劑，則使用任一組成者均可獲得良好之結果。為了確認此情況而進行了以下之實驗。As described above, in Experimental Examples 1 to 4, the polymer dispersant was produced by using the above-described method, but the present invention is not limited thereto, and it is included in all of the structural units as described above. ~45% by weight of the structural unit A represented by the general formula (1), 50 to 90% by weight of the structural unit B represented by the general formula (2), and relative to the structural unit B When the weight ratio (structural unit C/structural unit B) is 0.05 to 0.7 of the polymer dispersant of the copolymer of the structural unit C represented by the general formula (3), good results can be obtained by using any of the components. . In order to confirm this, the following experiment was conducted.
使用以下表7中所示之原料及投入量，利用與實驗例1中所準備之高分子分散劑之情形相同的方法，製造幾種高分子分散劑。再者，表7所示之高分子分散劑DA1~DA9中，高分子分散劑DA1係實驗例1~4中所使用之高分子分散劑。又，高分子分散劑DA12~DA14係本發明之範圍以外者。Several polymer dispersants were produced by the same method as in the case of the polymer dispersing agent prepared in Experimental Example 1 using the raw materials and the amounts shown in Table 7 below. Further, among the polymer dispersants DA1 to DA9 shown in Table 7, the polymer dispersant DA1 is a polymer dispersant used in Experimental Examples 1 to 4. Further, the polymer dispersants DA12 to DA14 are outside the scope of the present invention.
表7中，「MAA」為甲基丙烯酸，「PEGMA」為甲氧基聚乙二醇甲基丙烯酸酯，「SMA」為甲基丙烯酸硬脂基酯，「MMA」為甲基丙烯酸甲酯，「St」為苯乙烯，「IPA」為異丙醇，「MPD」為3-巰基-1,2-丙二醇。又，「PEGMA」中，「PEGMA(4)」係氧化乙烯之平均加成莫耳數為4之甲氧基聚乙二醇甲基丙烯酸酯，「PEGMA(9)」係氧化乙烯之平均加成莫耳數為9之甲氧基聚乙二醇甲基丙烯酸酯，「PEGMA(23)」係氧化乙烯之平均加成莫耳數為23之甲氧基聚乙二醇甲基丙烯酸酯。In Table 7, "MAA" is methacrylic acid, "PEGMA" is methoxy polyethylene glycol methacrylate, "SMA" is stearyl methacrylate, and "MMA" is methyl methacrylate. "St" is styrene, "IPA" is isopropanol, and "MPD" is 3-mercapto-1,2-propanediol. Further, in "PEGMA", "PEGMA (4)" is an average addition of ethylene oxide having a molar content of 4 methoxy polyethylene glycol methacrylate, and "PEGMA (9)" is an average of ethylene oxide. The methoxypolyethylene glycol methacrylate having a molar number of 9 and the "PEGMA (23)" ethylene oxide having an average addition molar amount of 23 methoxy polyethylene glycol methacrylate.
表7中亦表示有各高分子分散劑之重量平均分子量及不揮發成分。Table 7 also shows the weight average molecular weight and nonvolatile content of each of the polymer dispersants.
另一方面，準備平均粒徑為200nm(BET(Brunauer-Emmett-Teller)比表面積為5m2 /g)之鈦酸鋇粉末、及平均粒徑為100nm(BET比表面積為10m2 /g)之鈦酸鋇粉末。On the other hand, a barium titanate powder having an average particle diameter of 200 nm (BET (Brunauer-Emmett-Teller) specific surface area of 5 m 2 /g) and an average particle diameter of 100 nm (BET specific surface area of 10 m 2 /g) were prepared. Barium titanate powder.
繼而，使用上述高分子分散劑及各鈦酸鋇粉末，如下製作表8所示之試樣1~11之各陶瓷漿料。Then, using the above polymer dispersant and each barium titanate powder, each of the ceramic slabs of the samples 1 to 11 shown in Table 8 was produced as follows.
將鈦酸鋇粉末36g及高分子分散劑0.3g(有效成分)、與直徑為1mm之氧化鋯製之磨球150g一同投入至250mL之容器中，加入甲苯/乙醇=48/52(容積比)之混合液進行調整，以使得鈦酸鋇之固形物成分濃度達到30%。繼而，將容器於Paint Shaker(淺田鐵工公司製造)中振動1小時，使容器內之物質粉碎‧分散，獲得試樣1~11之各陶瓷漿料。36 g of barium titanate powder, 0.3 g of polymer dispersant (active ingredient), and 150 g of a ball of zirconia having a diameter of 1 mm were placed in a 250 mL container, and toluene/ethanol = 48/52 (volume ratio) was added. The mixture was adjusted so that the solid content of barium titanate was 30%. Then, the container was shaken in a Paint Shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour, and the contents of the container were pulverized and dispersed to obtain ceramic granules of the samples 1 to 11.
繼而，使用基於光子相關法(動態光散射法)之原理的Sysmex公司製造之粒度分布測定機「Zetasizer Nano ZS」，測定陶瓷漿料中之鈦酸鋇粒子之粒徑，分別求出D50及D90，並且計算出D90/D50之比。結果表示，D50之值越接近所使用之鈦酸鋇粉末之平均粒徑，或D90/D50之比越小，即粒徑分布越窄，則分散性越優異。Then, the particle size distribution measuring machine "Zetasizer Nano ZS" manufactured by Sysmex Co., Ltd. based on the principle of photon correlation method (dynamic light scattering method) was used to measure the particle size of the barium titanate particles in the ceramic slurry, and D50 and D90 were respectively determined. And calculate the ratio of D90/D50. As a result, the closer the value of D50 is to the average particle diameter of the barium titanate powder used, or the smaller the ratio of D90/D50, that is, the narrower the particle size distribution, the more excellent the dispersibility.
上述結果示於以下表8。The above results are shown in Table 8 below.
如表8所示，使用高分子分散劑DA1~DA11之試樣1~15之陶瓷漿料中，D50之值均接近於鈦酸鋇之平均粒徑，D90/D50之比亦均為2.1以下。As shown in Table 8, in the ceramic slurry of Samples 1 to 15 using the polymer dispersants DA1 to DA11, the value of D50 was close to the average particle diameter of barium titanate, and the ratio of D90/D50 was also 2.1 or less. .
相對於此，使用C/B重量比為0.05~0.7之範圍以外之高分子分散劑DA12~DA14的試樣16及17之陶瓷漿料中，D50之值雖然接近於鈦酸鋇之平均粒徑，但大於上述試樣1~15，而且D90/D50之比為較大之2.9以上。On the other hand, in the ceramic slurry of Samples 16 and 17 in which the polymer dispersant DA12 to DA14 having a C/B weight ratio of 0.05 to 0.7 was used, the value of D50 was close to the average particle diameter of barium titanate. However, it is larger than the above samples 1 to 15, and the ratio of D90/D50 is 2.9 or more.
又，使用不含有結構單元A之高分子分散劑DA14的試樣18之陶瓷漿料中，D50之值遠遠大於鈦酸鋇之平均粒徑。Further, in the ceramic slurry of the sample 18 which did not contain the polymer dispersant DA14 of the structural unit A, the value of D50 was much larger than the average particle diameter of barium titanate.
由以上可知，試樣1~15之陶瓷漿料的分散性較試樣16~18之陶瓷漿料的分散性優異。因此可理解，本發明中的高分子分散劑並不限於實驗例1~4中所使用之高分子分散劑，只要為如上所示般包含含有全部結構單元中之5~45重量%的以通式(1)所示之結構單元A、全部結構單元中之50~90重量%的以通式(2)所示之結構單元B、及以相對於結構單元B之重量比(結構單元C/結構單元B)計為0.05~0.7的以通式(3)所示之結構單元C的共聚物之高分子分散劑，則使用任一組成者時，關於陶瓷生片之表面粗糙度、密度比及斷裂強度，以及關於積層陶瓷電容器之短路發生率等均可獲得良好之結果。From the above, it was found that the dispersibility of the ceramic slurry of Samples 1 to 15 was superior to that of the ceramic slurry of Samples 16 to 18. Therefore, it is understood that the polymer dispersant in the present invention is not limited to the polymer dispersant used in Experimental Examples 1 to 4, and as long as it contains 5 to 45% by weight of all the structural units as described above. 50 to 90% by weight of the structural unit A represented by the formula (1), the structural unit B represented by the general formula (2), and the weight ratio relative to the structural unit B (structural unit C/) The structural unit B) is a polymer dispersing agent of a copolymer of the structural unit C represented by the formula (3) in the range of 0.05 to 0.7, and the surface roughness and density ratio of the ceramic green sheet are used when any of the constituents is used. Good results can be obtained with the breaking strength and the occurrence rate of the short circuit of the laminated ceramic capacitor.
1．．．積層陶瓷電容器1. . . Multilayer ceramic capacitor
2．．．陶瓷層2. . . Ceramic layer
3、4．．．內部導體膜3, 4. . . Inner conductor film
5．．．陶瓷積層體5. . . Ceramic laminate
圖1係表示作為利用本發明之製造方法而製造的積層型陶瓷電子零件之一例之積層陶瓷電容器1的剖面圖。Fig. 1 is a cross-sectional view showing a multilayer ceramic capacitor 1 as an example of a laminated ceramic electronic component manufactured by the manufacturing method of the present invention.
圖2係對實驗例1中所製作之實施例及比較例之各陶瓷漿料，表示球磨機處理時間與各陶瓷漿料中之陶瓷粒子之平均粒徑(D50)之關係的圖。Fig. 2 is a graph showing the relationship between the treatment time of the ball mill and the average particle diameter (D50) of the ceramic particles in each ceramic slurry in each of the ceramic pastes of the examples and comparative examples produced in Experimental Example 1.
1．．．積層陶瓷電容器1. . . Multilayer ceramic capacitor
2．．．陶瓷層2. . . Ceramic layer
3、4．．．內部導體膜3, 4. . . Inner conductor film
5．．．陶瓷積層體5. . . Ceramic laminate
6、7．．．外部端子電極6, 7. . . External terminal electrode
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008217540 | 2008-08-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201010963A TW201010963A (en) | 2010-03-16 |
| TWI432397B true TWI432397B (en) | 2014-04-01 |
Family
ID=41721356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW98128253A TWI432397B (en) | 2008-08-27 | 2009-08-21 | Ceramic manufacturing and laminated ceramic electronic parts manufacturing method |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5267565B2 (en) |
| CN (1) | CN102123968A (en) |
| TW (1) | TWI432397B (en) |
| WO (1) | WO2010024188A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5666941B2 (en) * | 2010-02-26 | 2015-02-12 | 花王株式会社 | Slurry composition containing basic ceramics |
| JP5316615B2 (en) * | 2011-09-07 | 2013-10-16 | 株式会社村田製作所 | Multilayer ceramic electronic components |
| KR101452186B1 (en) * | 2012-12-26 | 2014-10-21 | 주식회사 누리비스타 | Paste for internal electrode and multi-layer ceramic capacitor using the same |
| WO2015040924A1 (en) * | 2013-09-18 | 2015-03-26 | 株式会社村田製作所 | Ceramic molded body, and method for producing stacked ceramic electronic component |
| WO2019188775A1 (en) * | 2018-03-28 | 2019-10-03 | 住友金属鉱山株式会社 | Electrically conductive paste, electronic component, and laminated ceramic capacitor |
| EP4130147A4 (en) | 2020-03-30 | 2023-08-09 | FUJIFILM Corporation | Composition, film, and optical sensor |
| CN112992431B (en) * | 2021-04-16 | 2021-08-03 | 西安宏星电子浆料科技股份有限公司 | High-dispersion nickel inner electrode slurry for multilayer chip ceramic capacitor and preparation method thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60155567A (en) * | 1984-01-24 | 1985-08-15 | 日立化成工業株式会社 | Manufacture of binder bor ceramic |
| JPH08217549A (en) * | 1995-02-09 | 1996-08-27 | Murata Mfg Co Ltd | Ceramic slurry composition |
| JP3378133B2 (en) * | 1995-12-27 | 2003-02-17 | ライオン株式会社 | Ceramic molding binder |
| JP3812243B2 (en) * | 1999-10-18 | 2006-08-23 | 株式会社村田製作所 | Manufacturing method of ceramic green sheet with carrier film |
| JP3823759B2 (en) * | 2000-06-29 | 2006-09-20 | 株式会社村田製作所 | Method for producing ceramic slurry composition |
| JP2003104779A (en) * | 2001-09-28 | 2003-04-09 | Nisshin Chem Ind Co Ltd | Aqueous solution type binder for ceramic molding |
| JP3902603B2 (en) * | 2004-03-25 | 2007-04-11 | 日立金属株式会社 | Multilayer ceramic substrate manufacturing method and restraint sheet |
| JP5109276B2 (en) * | 2006-03-29 | 2012-12-26 | 日油株式会社 | Slurry composition for ceramic production |
| JP2008024553A (en) * | 2006-07-21 | 2008-02-07 | Sanyo Chem Ind Ltd | Dispersant for extrusion molding ceramic |
-
2009
- 2009-08-21 JP JP2010526674A patent/JP5267565B2/en active Active
- 2009-08-21 TW TW98128253A patent/TWI432397B/en active
- 2009-08-21 WO PCT/JP2009/064614 patent/WO2010024188A1/en active Application Filing
- 2009-08-21 CN CN2009801319647A patent/CN102123968A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP5267565B2 (en) | 2013-08-21 |
| CN102123968A (en) | 2011-07-13 |
| JPWO2010024188A1 (en) | 2012-01-26 |
| TW201010963A (en) | 2010-03-16 |
| WO2010024188A1 (en) | 2010-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI432397B (en) | Ceramic manufacturing and laminated ceramic electronic parts manufacturing method | |
| TWI477576B (en) | Conductive paste, and laminated ceramic electronic parts and manufacturing method thereof | |
| JP3823759B2 (en) | Method for producing ceramic slurry composition | |
| WO2014084273A1 (en) | Paste composition, and sintered body and method for producing same | |
| JP6511109B2 (en) | Conductive paste | |
| CN111868842B (en) | Conductive paste with stable viscosity over time | |
| TW202034352A (en) | Conductive paste, electronic component, and laminated ceramic capacitor | |
| JP4403920B2 (en) | Method for producing release layer paste and method for producing multilayer electronic component | |
| CN110168021A (en) | Paste compound, ceramic green sheet and coated sheet | |
| JP2010067418A (en) | Conductive paste and method of manufacturing the same | |
| TWI248457B (en) | Water-soluble acrylic binder, method for producing the same, ceramic slurry composition, method for producing the same, laminate ceramic electronic part and method for manufacturing the same | |
| TWI838578B (en) | Conductive paste and method for producing electronic parts using the same | |
| TW201518250A (en) | Ceramic molded body, and method for producing stacked ceramic electronic component | |
| JP6856701B2 (en) | Manufacturing method of paste for internal electrodes and laminated ceramic electronic components | |
| TWI297341B (en) | A copolymer which is used as a dispersing agent for titanate-based ceramic colloids | |
| TWI838464B (en) | Conductive paste | |
| CN107452435B (en) | Paste for forming conductor | |
| JP5976559B2 (en) | Nanoparticulate barium titanate and method for producing the same | |
| JP7180282B2 (en) | Metal oxide nanoparticle dispersion for firing and method for producing sintered film | |
| JP2002255657A (en) | Ceramic slurry, ceramic green sheet and multi-layered ceramic electronic parts | |
| JP2006080496A (en) | Paste for releasable layer, and method of manufacturing laminated electronic component | |
| US12006266B2 (en) | Baking slurry composition, green sheet, method for manufacturing green sheet, method for manufacturing sintered product, and method for manufacturing monolithic ceramic capacitor | |
| JP4817633B2 (en) | Method for preparing ceramic slurry and method for producing ceramic | |
| KR100593888B1 (en) | Method for Manufacturing a Hybrid Sol for Producing a Laminate of High-Capacity Multilayer Ceramic Capacitor and the Hybrid Sol therefrom | |
| TWI447133B (en) | Anionic copolymer and ceramic composition containing the same |