JPWO2010024188A1 - Method for manufacturing ceramic molded body and multilayer ceramic electronic component - Google Patents
Method for manufacturing ceramic molded body and multilayer ceramic electronic component Download PDFInfo
- Publication number
- JPWO2010024188A1 JPWO2010024188A1 JP2010526674A JP2010526674A JPWO2010024188A1 JP WO2010024188 A1 JPWO2010024188 A1 JP WO2010024188A1 JP 2010526674 A JP2010526674 A JP 2010526674A JP 2010526674 A JP2010526674 A JP 2010526674A JP WO2010024188 A1 JPWO2010024188 A1 JP WO2010024188A1
- Authority
- JP
- Japan
- Prior art keywords
- ceramic
- structural unit
- molded body
- weight
- dispersant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 283
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 238000000034 method Methods 0.000 title description 17
- 239000002245 particle Substances 0.000 claims abstract description 77
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000004815 dispersion polymer Substances 0.000 claims abstract description 4
- 239000002270 dispersing agent Substances 0.000 claims description 76
- 239000000843 powder Substances 0.000 claims description 50
- 229920000642 polymer Polymers 0.000 claims description 41
- 239000002002 slurry Substances 0.000 claims description 40
- 239000002994 raw material Substances 0.000 claims description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 239000004020 conductor Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000003985 ceramic capacitor Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 20
- 229910002113 barium titanate Inorganic materials 0.000 description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- 230000003746 surface roughness Effects 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- -1 2-ethoxyethyl Chemical group 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000012856 packing 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
- 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000002474 experimental method 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
- 229920002818 (Hydroxyethyl)methacrylate Polymers 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
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-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
- 238000005054 agglomeration Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution 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
- 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
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000012545 processing Methods 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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 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
- 239000003153 chemical reaction reagent Substances 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
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 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
- 150000002500 ions Chemical class 0.000 description 2
- 238000010030 laminating Methods 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
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 239000000243 solution Substances 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
- 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
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 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
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 101001062854 Rattus norvegicus Fatty acid-binding protein 5 Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000007869 azo polymerization initiator Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 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
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000014759 maintenance of location 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
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-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
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 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
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
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)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Ceramic Capacitors (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
セラミックグリーンシートにおいてセラミック粒子が微粒化されても凝集しにくくして、セラミック層の薄層化が図られてもショート不良などを発生しにくくする。セラミック層２となるべきセラミックグリーンシートにおいて、セラミック粒子の表面を、下記一般式（１）で示される構成単位Ａを全構成単位中５〜４５重量％、一般式（２）で示される構成単位Ｂを全構成単位中５０〜９０重量％、および一般式（３）で示される構成単位Ｃを構成単位Ｂに対する重量比で０．０５〜０．７含有する、共重合体からなる高分子分散剤によって覆うようにする。【化１】Even if the ceramic particles are atomized in the ceramic green sheet, it is difficult to agglomerate, and even if the ceramic layer is thinned, it is difficult to cause a short circuit defect or the like. In the ceramic green sheet to be the ceramic layer 2, the surface of the ceramic particles is composed of 5 to 45% by weight of the structural unit A represented by the following general formula (1) in the total structural unit and the structural unit represented by the general formula (2). Polymer dispersion comprising a copolymer containing B in an amount of 50 to 90% by weight in all the structural units and 0.05 to 0.7 in a weight ratio of the structural unit C represented by the general formula (3) to the structural unit B Cover with an agent. [Chemical 1]
Description
この発明は、セラミック成形体および積層型セラミック電子部品の製造方法に関するもので、特に、積層型セラミック電子部品におけるセラミック層を形成するために好適に用いられ得るセラミック成形体およびこれを用いて実施される積層型セラミック電子部品の製造方法に関するものである。 The present invention relates to a ceramic molded body and a method for producing a multilayer ceramic electronic component, and in particular, a ceramic molded body that can be suitably used for forming a ceramic layer in a multilayer ceramic electronic component, and the ceramic molded body. The present invention relates to a method for manufacturing a multilayer ceramic electronic component.
積層セラミックコンデンサに代表される積層型セラミック電子部品は、複数のセラミック層と複数の内部電極とを交互に積層した構造を有する、セラミック積層体を備えている。セラミック層を形成するため、セラミックスラリーが用意されるが、セラミック積層体を得るにあたっては、セラミックスラリーをシート状に成形することによって得られるセラミックグリーンシートを予め作製してから、これら複数のセラミックグリーンシートを積み重ねたり、セラミックスラリーを印刷、乾燥することを繰り返したりすることを行なっている。 A multilayer ceramic electronic component typified by a multilayer ceramic capacitor includes a ceramic multilayer body having a structure in which a plurality of ceramic layers and a plurality of internal electrodes are alternately stacked. In order to form a ceramic layer, a ceramic slurry is prepared. In order to obtain a ceramic laminate, a ceramic green sheet obtained by forming a ceramic slurry into a sheet shape is prepared in advance, and then the plurality of ceramic greens are prepared. Sheets are stacked, and ceramic slurry is repeatedly printed and dried.
ここで用いられるセラミックスラリーにおいては、溶剤中にセラミック原料粉末とバインダ成分とを均一に分散させることが重要であり、そのために、セラミック原料粉末の表面に吸着して分散性を向上させるための不飽和脂肪酸などの分散剤が添加されている（たとえば、特許文献１参照）。 In the ceramic slurry used here, it is important to uniformly disperse the ceramic raw material powder and the binder component in the solvent. For this reason, it is necessary to adsorb on the surface of the ceramic raw material powder to improve the dispersibility. A dispersant such as a saturated fatty acid is added (see, for example, Patent Document 1).
近年、積層セラミックコンデンサであれば大静電容量化というように、積層型セラミック電子部品の特性を向上させるために、積層型セラミック電子部品に備えるセラミック層が薄層化され、それによって、積層枚数が増加されることが求められている。この薄層化の要求に応えるためには、そこに含まれるセラミック原料粉末の粒径をたとえば１００ｎｍ以下というように微粒化する必要がある。 Recently, in order to improve the characteristics of multilayer ceramic electronic components, such as increasing the capacitance of multilayer ceramic capacitors, the ceramic layer provided for multilayer ceramic electronic components has been made thinner, thereby increasing the number of laminated ceramic capacitors. Is required to be increased. In order to meet the demand for thinning, it is necessary to make the particle size of the ceramic raw material powder contained therein fine, for example, 100 nm or less.
しかしながら、セラミック原料粉末の微粒化を進めれば進めるほど、セラミックスラリー中において、セラミック原料粉末同士が凝集しやすくなるため、セラミック原料粉末の分散性が悪化してしまう。このように、分散性が悪化したセラミック原料粉末を含むセラミックスラリーを用いてセラミック層を形成しながら、セラミック積層体を作製すると、各セラミック層の密度が低下したり、表面粗さが悪化したりして、得られた積層型セラミック電子部品において、ショート不良や絶縁不良といった不具合が生じてしまうことがある。 However, the further the atomization of the ceramic raw material powder is, the more easily the ceramic raw material powders are aggregated in the ceramic slurry, so that the dispersibility of the ceramic raw material powder is deteriorated. In this way, when a ceramic laminate is produced while forming a ceramic layer using a ceramic slurry containing a ceramic raw material powder whose dispersibility has deteriorated, the density of each ceramic layer is reduced or the surface roughness is deteriorated. As a result, in the obtained multilayer ceramic electronic component, problems such as short circuit failure and insulation failure may occur.
なお、セラミック原料粉末同士の凝集を防止するためには、前述の分散剤の添加量を多くすることも考えられるが、このように分散剤を過剰添加すると、セラミック原料粉末同士の凝集はある程度抑制できるものの、セラミックグリーンシートのようなセラミック成形体中におけるセラミック原料粉末の充填密度が低下するばかりでなく、バインダ成分によるセラミック原料粉末間の結合力が低下し、その結果、セラミック成形体の強度が低下してしまう。 In order to prevent agglomeration between ceramic raw material powders, it may be possible to increase the amount of the above-mentioned dispersant added. However, if the dispersant is added excessively in this way, agglomeration between ceramic raw material powders is suppressed to some extent. Although not only the packing density of the ceramic raw material powder in the ceramic green body such as the ceramic green sheet is reduced, but also the bonding force between the ceramic raw material powders due to the binder component is reduced, and as a result, the strength of the ceramic green body is reduced. It will decline.
そこで、この発明の目的は、上述したようなセラミック原料粉末同士の凝集によって引き起こされる問題を解決し得る、セラミック成形体を提供しようとすることである。 Accordingly, an object of the present invention is to provide a ceramic molded body that can solve the problems caused by the aggregation of ceramic raw material powders as described above.
この発明の他の目的は、上述したセラミック成形体を用いて実施される、積層型セラミック電子部品の製造方法を提供しようとすることである。 Another object of the present invention is to provide a method for manufacturing a multilayer ceramic electronic component, which is carried out using the ceramic molded body described above.
この発明は、セラミック原料粉末とバインダ成分と溶剤とを含むセラミックスラリーに所定の形状を付与することによって得られた、セラミック成形体にまず向けられる。上述した技術的課題を解決するため、セラミック原料粉末を構成するセラミック粒子の表面が分散剤によって覆われていて、この分散剤は、下記一般式（１）で示される構成単位Ａを全構成単位中５〜４５重量％、下記一般式（２）で示される構成単位Ｂを全構成単位中５０〜９０重量％、および、下記一般式（３）で示される構成単位Ｃを構成単位Ｂに対する重量比（構成単位Ｃ／構成単位Ｂ）で０．０５〜０．７含有する、共重合体からなる高分子分散剤を含むものである。 The present invention is first directed to a ceramic molded body obtained by imparting a predetermined shape to a ceramic slurry containing a ceramic raw material powder, a binder component, and a solvent. In order to solve the technical problem described above, the surface of the ceramic particles constituting the ceramic raw material powder is covered with a dispersant, and this dispersant is composed of all the structural units A represented by the following general formula (1). 5 to 45% by weight, the structural unit B represented by the following general formula (2) is 50 to 90% by weight of all the structural units, and the structural unit C represented by the following general formula (3) is the weight relative to the structural unit B. It contains a polymer dispersant composed of a copolymer, which is contained in a ratio (constituent unit C / constituent unit B) of 0.05 to 0.7.
上記式（１）および（２）において、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５およびＲ６は同一または異なり、水素原子または炭素数１〜２のアルキル基を示し、Ｒ７は炭素数１〜４の直鎖または分岐鎖のアルキレン基を示し、Ｒ８は水素原子または炭素数１〜２のアルキル基を示し、Ｘ１は酸素原子またはＮＨを示し、Ｍは水素原子または陽イオンを示し、ｎは１〜５０の数を示す。In the above formulas (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 is A linear or branched alkylene group having 1 to 4 carbon atoms, R 8 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, X 1 represents an oxygen atom or NH, and M represents a hydrogen atom or a positive chain. Represents an ion, and n represents a number of 1 to 50.
上記式（３）において、Ｒ９、Ｒ１０およびＲ１１は同一または異なり、水素原子または炭素数１〜２のアルキル基を示し、Ｘ２は酸素原子またはＮＨを示し、Ｒ１２およびＲ１３は炭素数１〜３０の直鎖、分岐鎖もしくは環状のアルキル基もしくはアルケニル基またはアリール基を示す。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 linear, branched or cyclic alkyl group, alkenyl group or aryl group having 1 to 30 carbon atoms is shown.
この発明に係るセラミック成形体において、セラミック粒子の径が１０ｎｍ〜３００ｎｍというように、セラミック粒子が微粒化されることが好ましい。このように、セラミック粒子の径が１０ｎｍ〜３００ｎｍの範囲にあるとき、高分子分散剤の添加量は、セラミック粒子１００重量部に対して、０．１〜１０重量部であることが好ましい。 In the ceramic molded body according to the present invention, the ceramic particles are preferably atomized so that the diameter of the ceramic particles is 10 nm to 300 nm. Thus, when the diameter of the ceramic particles is in the range of 10 nm to 300 nm, the addition amount of the polymer dispersant is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the ceramic particles.
この発明は、また、積層された複数のセラミックグリーン層およびセラミックグリーン層間の特定の界面に沿って形成された内部導体膜を備える、生のセラミック積層体を作製する工程と、生のセラミック積層体を焼成する工程とを備える、積層型セラミック電子部品の製造方法にも向けられる。この発明に係る積層型セラミック電子部品の製造方法において、上記生のセラミック積層体に備えるセラミックグリーン層は、この発明に係るセラミック成形体からなることを特徴としている。 The present invention also includes a step of producing a raw ceramic laminate comprising a plurality of laminated ceramic green layers and an inner conductor film formed along a specific interface between the ceramic green layers, and a raw ceramic laminate. And a method for producing a multilayer ceramic electronic component. In the method for manufacturing a multilayer ceramic electronic component according to the present invention, the ceramic green layer provided in the raw ceramic multilayer body is formed of the ceramic molded body according to the present invention.
この発明に係る積層型セラミック電子部品の製造方法において、生のセラミック積層体を作製するにあたっては、第１の実施態様では、セラミックグリーン層を与えるセラミック成形体からなる複数のセラミックグリーンシートを作製する工程と、複数のセラミックグリーンシートを積み重ねる工程とが実施され、第２の実施態様では、セラミック成形体を構成するセラミックスラリーを塗布する工程を繰り返すことによって、積層された複数のセラミックグリーン層を形成する工程が実施される。 In the method for producing a multilayer ceramic electronic component according to the present invention, when producing a raw ceramic laminate, in the first embodiment, a plurality of ceramic green sheets made of a ceramic molded body providing a ceramic green layer are produced. And a step of stacking a plurality of ceramic green sheets are performed, and in the second embodiment, a plurality of laminated ceramic green layers are formed by repeating the step of applying a ceramic slurry constituting the ceramic molded body. The process of carrying out is performed.
この発明によれば、前述したような高分子分散剤を用いることによって、適度な添加量でセラミック原料粉末の表面を分散剤によって均一にかつ効率的に覆わせることができるため、凝集しやすい微粒のセラミック原料粉末を用いても、凝集が抑制され、充填率の高いセラミック成形体とすることができる。 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 covered with the dispersant with an appropriate addition amount. Even if this ceramic raw material powder is used, agglomeration is suppressed and a ceramic compact having a high filling rate can be obtained.
したがって、このようなセラミック成形体を構成するセラミックスラリーを用いて積層型セラミック電子部品を作製すれば、ショート不良や絶縁不良などの不良発生率を大幅に低減することができる。 Therefore, if a multilayer ceramic electronic component is produced using the ceramic slurry constituting such a ceramic molded body, the occurrence rate of defects such as short-circuit defects and insulation defects can be greatly reduced.
この発明に係るセラミック成形体は、前述したように、セラミック原料粉末とバインダ成分と溶剤とを含んでいる。セラミック原料粉末の集合体には所定の形状が付与され、このセラミック原料粉末の集合体に付与された所定の形状がバインダによって維持されている。 As described above, the ceramic molded body according to the present invention includes ceramic raw material powder, a binder component, and a solvent. A predetermined shape is imparted to the aggregate of ceramic raw material powders, and the predetermined shape imparted to the aggregate of ceramic raw material powders is maintained by a binder.
セラミック原料粉末同士の凝集を防止するため、セラミック原料粉末を構成するセラミック粒子の表面が分散剤によって覆われている。この分散剤は、下記一般式（１）で示される構成単位Ａを全構成単位中５〜４５重量％、下記一般式（２）で示される構成単位Ｂを全構成単位中５０〜９０重量％、および、下記一般式（３）で示される構成単位Ｃを構成単位Ｂに対する重量比（構成単位Ｃ／構成単位Ｂ）で０．０５〜０．７含有する、共重合体からなる高分子分散剤を含んでいる。 In order to prevent aggregation of the ceramic raw material powders, the surfaces of the ceramic particles constituting the ceramic raw material powder are covered with a dispersant. In this dispersant, the structural unit A represented by the following general formula (1) is 5 to 45% by weight in all the structural units, and the structural unit B represented by the following general formula (2) is 50 to 90% by weight in all the structural units. And a polymer dispersion comprising a copolymer containing 0.05 to 0.7 of the structural unit C represented by the following general formula (3) in a weight ratio to the structural unit B (structural unit C / structural unit B) Contains agents.
上記式（１）および（２）において、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５およびＲ６は同一または異なり、水素原子または炭素数１〜２のアルキル基を示し、Ｒ７は炭素数１〜４の直鎖または分岐鎖のアルキレン基を示し、Ｒ８は水素原子または炭素数１〜２のアルキル基を示し、Ｘ１は酸素原子またはＮＨを示し、Ｍは水素原子または陽イオンを示し、ｎは１〜５０の数を示す。In the above formulas (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 is A linear or branched alkylene group having 1 to 4 carbon atoms, R 8 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, X 1 represents an oxygen atom or NH, and M represents a hydrogen atom or a positive chain. Represents an ion, and n represents a number of 1 to 50.
上記式（３）において、Ｒ９、Ｒ１０およびＲ１１は同一または異なり、水素原子または炭素数１〜２のアルキル基を示し、Ｘ２は酸素原子またはＮＨを示し、Ｒ１２およびＲ１３は炭素数１〜３０の直鎖、分岐鎖もしくは環状のアルキル基もしくはアルケニル基またはアリール基を示す。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 linear, branched or cyclic alkyl group, alkenyl group or aryl group having 1 to 30 carbon atoms is shown.
この高分子分散剤は、たとえば、上記構成単位Ａとなるカルボキシル基などの中和可能な酸性基を有する酸性モノマーや重合後に中和可能な酸性基を付加できるモノマーと、上記構成単位Ｂとなる非イオン性モノマーや重合後に非イオン性基を導入できるモノマーと、上記構成単位Ｃとなる疎水性モノマーとを含む、モノマー成分を溶液重合法で重合させるなど、公知の方法で得ることができる。 This polymer dispersant is, for example, an acidic monomer having a neutralizable acidic group such as a carboxyl group to be the structural unit A, a monomer capable of adding a neutralizable acidic group after polymerization, and the structural unit B. It can be obtained by a known method such as polymerizing a monomer component containing a nonionic monomer or a monomer capable of introducing a nonionic group after polymerization and a hydrophobic monomer serving as the structural unit C by a solution polymerization method.
上記構成単位Ａとなる酸性モノマーとしては、たとえば、（メタ）アクリル酸、クロトン酸等が挙げられる。 As an acidic monomer used as the said structural unit A, (meth) acrylic acid, crotonic acid, etc. are mentioned, for example.
上記構成単位Ｂとなる非イオン性モノマーとしては、たとえば、メトキシポリエチレングリコール（メタ）アクリレート、メトキシポリ（エチレングリコール／プロピレングリコール）モノ（メタ）アクリレート、エトキシポリ（エチレングリコール／プロピレングリコール）モノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、２−メトキシエチル（メタ）アクリルアミド、２−エトキシエチル（メタ）アクリルアミド、３−メトキシプロピル（メタ）アクリルアミド等が挙げられる。 Examples of the nonionic monomer that constitutes the structural unit B include methoxypolyethylene glycol (meth) acrylate, methoxypoly (ethylene glycol / propylene glycol) mono (meth) acrylate, and ethoxypoly (ethylene glycol / propylene glycol) mono (meth) acrylate. Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-methoxyethyl (meth) acrylamide, 2-ethoxyethyl (meth) acrylamide, 3-methoxypropyl (meth) acrylamide and the like.
上記構成単位Ｃとなる疎水性モノマーとしては、たとえば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、オクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベヘニル（メタ）アクリレート等のエステル化合物、ブチル（メタ）アクリルアミド、オクチル（メタ）アクリルアミド、ラウリル（メタ）アクリルアミド、ステアリル（メタ）アクリルアミド、ベヘニル（メタ）アクリルアミド等のアミド化合物、１−デセン、１−オクタデセン等のα−オレフィンおよびスチレン等が挙げられる。 Examples of the hydrophobic monomer serving as the structural unit C include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, Ester compounds such as behenyl (meth) acrylate, butyl (meth) acrylamide, octyl (meth) acrylamide, lauryl (meth) acrylamide, stearyl (meth) acrylamide, amide compounds such as behenyl (meth) acrylamide, 1-decene, 1- Examples include α-olefins such as octadecene and styrene.
溶液重合で用いられる溶媒としては、たとえば、芳香族炭化水素（トルエン、キシレン等）、低級アルコール（エタノール、イソプロパノール等）、ケトン（アセトン、メチルエチルケトン）、テトラヒドロフラン、ジエチレングリコール、ジメチルエーテル等の有機溶剤を用いることができる。溶媒量は、重量比で、モノマー全量の０．５〜１０倍であることが好ましい。 Examples of the solvent used in the solution polymerization include organic solvents such as aromatic hydrocarbons (toluene, xylene, etc.), lower alcohols (ethanol, isopropanol, etc.), ketones (acetone, methyl ethyl ketone), tetrahydrofuran, diethylene glycol, dimethyl ether, etc. Can do. The amount of solvent is preferably 0.5 to 10 times the total amount of monomers in terms of weight ratio.
重合開始剤としては、公知のラジカル重合開始剤を用いることができ、たとえば、アゾ系重合開始剤、ヒドロ過酸化物類、過酸化ジアルキル類、過酸化ジアシル類、ケトンペルオキシド類等が挙げられる。重合開始剤量は、モノマー成分全量に対し、０．０１〜５モル％が好ましく、０．０１〜３モル％がより好ましく、０．０１〜１モル％が最も好ましい。重合反応は、窒素気流下、６０〜１８０℃の温度範囲で行なうのが好ましく、反応時間は０．５〜２０時間が好ましい。 As the polymerization initiator, a known radical polymerization initiator can be used, and examples thereof include azo polymerization initiators, hydroperoxides, dialkyl peroxides, diacyl peroxides, and ketone peroxides. The amount of the polymerization initiator 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.
高分子分散剤において、構成単位Ａ、構成単位Ｂおよび構成単位Ｃの配列は、ランダム、ブロックおよびグラフトのいずれでもよい。また、前述の含有量の範囲をすべて満たすのであれば、これら構成単位Ａ〜Ｃ以外の構成単位を含んでいてもよい。 In the polymer dispersant, the arrangement of the structural unit A, the structural unit B, and the structural unit C may be random, block, or graft. Moreover, as long as all the above-mentioned content ranges are satisfied, structural units other than these structural units A to C may be included.
高分子分散剤の重量平均分子量は、セラミック原料粉末の分散性の観点から、１５０００〜２０００００が好ましく、２００００〜１０００００がより好ましい。ただし、セラミック原料粉末の平均粒径が１００ｎｍ未満の小粒径の場合は、高分子分散剤の重量平均分子量は、１０００〜１５０００未満が好ましく、２０００〜１００００がより好ましい。 The weight average molecular weight of the polymer dispersant is preferably 15,000 to 200,000, more preferably 20,000 to 100,000, from the viewpoint of dispersibility of the ceramic raw material powder. However, when the ceramic raw material powder has a small particle size 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.
なお、これら重量平均分子量はＧＰＣ（ゲルパーミエーションクロマトグラフィー）により測定した値である。 These weight average molecular weights are values measured by GPC (gel permeation chromatography).
一般に、非水系スラリーにおいては、セラミック粒子表面の塩基サイトと分散剤の酸性サイトとの相互作用により、セラミック粒子表面に分散剤が吸着するものと考えられている。セラミック粒子表面に吸着した分散剤は、立体障壁を形成し、セラミック粒子同士の凝集を抑制している。 In general, in a non-aqueous slurry, it is considered that the dispersant is adsorbed on the surface of the ceramic particle by the interaction between the base site on the surface of the ceramic particle and the acidic site of the dispersant. The dispersant adsorbed on the surface of the ceramic particles forms a three-dimensional barrier and suppresses aggregation of the ceramic particles.
前述した特許文献１に記載の技術では、セラミック粒子の表面全面に分散剤を吸着させようとする場合、吸着効率が悪く、かつ吸着した分散剤の保持能力が低いため、たとえば、セラミック粒子がその表面において塩基性を示す材料からなる場合、セラミック粒子表面の全塩基量と分散剤の全酸量とが等分になるよう調整しても、セラミック粒子表面に吸着していない分散剤が比較的多く残る。
In the technique described in
また、吸着した分散剤も、その構造によっては立体障壁が十分に機能せず、セラミック粒子同士の凝集抑制効果が不十分な場合がある。 In addition, the adsorbed dispersant may not have a sufficient steric barrier function depending on its structure, and may not sufficiently suppress the aggregation of ceramic particles.
分散剤が表面に吸着していないセラミック粒子が存在し、かつ吸着している分散剤の立体障壁が十分に機能しないとすると、そこを起点としてセラミック粒子同士が凝集し、セラミックスラリーの分散性が悪化する。このような不都合は、特に、セラミック粒子の粒径がたとえば１００ｎｍ以下と微粒化された場合に顕著となる。 If there are ceramic particles on which the dispersant is not adsorbed on the surface, and the steric barrier of the adsorbed dispersant does not function sufficiently, the ceramic particles aggregate from that point and the dispersibility of the ceramic slurry is reduced. Getting worse. Such inconvenience is particularly noticeable when the particle size of the ceramic particles is atomized to, for example, 100 nm or less.
これに対して、この発明に係るセラミック成形体によれば、そこに含まれる高分子分散剤の、セラミック粒子表面への吸着率が高く、かつ吸着した分散剤の保持能力が高く、さらに立体障壁としての機能が高い。そのため、このような高分子分散剤を過剰に添加する必要がなく、必要最低限の分散剤量によって、分散剤がセラミック粒子表面に吸着し、立体障壁を形成する状態とすることができる。よって、セラミック粒子の粒径がたとえば１００ｎｍ以下と微粒化されても、セラミックスラリー中のセラミック原料粉末の凝集が抑制され、セラミック原料粉末が均一に分散した状態にあるセラミック成形体を得ることができる。 On the other hand, according to the ceramic molded body according to the present invention, the polymer dispersant contained therein has a high adsorption rate to the surface of the ceramic particles and has a high ability to hold the adsorbed dispersant, and further a three-dimensional barrier. As a high function. Therefore, it is not necessary to add an excessive amount of such a polymer dispersant, and the dispersant can be adsorbed on the surface of the ceramic particles and form a steric barrier with a minimum amount of the dispersant. Therefore, even if the particle size of the ceramic particles is reduced to, for example, 100 nm or less, aggregation of the ceramic raw material powder in the ceramic slurry is suppressed, and a ceramic molded body in which the ceramic raw material powder is uniformly dispersed can be obtained. .
その結果、セラミック成形体中のセラミック原料粉末の充填密度を高くすることができ、セラミック成形体の密度を高くすることができる。また、セラミック成形体中において分散剤が占める割合を低くすることができるため、セラミック成形体の強度を増すことができる。 As a result, the packing density of the ceramic raw material powder in the ceramic molded body can be increased, and the density of the ceramic molded body can be increased. Moreover, since the ratio for which a dispersing agent accounts in a ceramic molded object can be made low, the intensity | strength of a ceramic molded object can be increased.
また、この発明において用いられる高分子分散剤は、吸着効率が高いことから、短時間で分散処理を終了させることができる。よって、生産性を向上させることができるとともに、分散処理中にセラミック原料粉末が受けるダメージの低減を図ることができる。そのため、セラミック原料粉末が本来持つ結晶性を維持したまま、セラミック成形体を提供することができる。 Further, since the polymer dispersant used in the present invention has 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 during the dispersion treatment can be reduced. Therefore, a ceramic molded body can be provided while maintaining the crystallinity inherent to the ceramic raw material powder.
この発明に係るセラミック成形体の一実施形態は、積層型セラミック電子部品を製造する際に用意されるセラミックグリーンシートである。 One embodiment of the ceramic molded body according to the present invention is a ceramic green sheet prepared when manufacturing a multilayer ceramic electronic component.
図１は、この発明に係る製造方法によって製造される積層型セラミック電子部品の一例としての積層セラミックコンデンサ１を示す断面図である。
FIG. 1 is a cross-sectional view showing a multilayer
積層セラミックコンデンサ１は、積層された複数のセラミック層２とセラミック層２間の特定の界面に沿って形成される複数の内部導体膜３および４とをもって構成される、セラミック積層体５を備えている。
The multilayer
セラミック積層体５の外表面上の互いに異なる位置には、第１および第２の外部端子電極６および７が形成される。図１に示した積層セラミックコンデンサ１では、第１および第２の外部端子電極６および７は、セラミック積層体５の互いに対向する各端面上に形成される。内部導体膜３および４は、第１の外部端子電極６に電気的に接続される第１の内部導体膜３と第２の外部端子電極７に電気的に接続される第２の内部導体膜４とがあり、これら第１および第２の内部導体膜３および４は、積層方向に関して交互に配置されている。
First and second
上述した積層セラミックコンデンサ１を製造するため、セラミック積層体５の生の状態のものが作製される。生のセラミック積層体は、セラミック層２となるべき積層された複数のセラミックグリーン層を備え、セラミックグリーン層間の特定の界面に沿って内部導体膜３および４が形成されている。次いで、生のセラミック積層体が焼成されることによって、焼結したセラミック積層体５が得られ、その後、外部端子電極６および７が形成されることによって、積層セラミックコンデンサ１が完成される。
In order to manufacture the multilayer
上述の生のセラミック積層体において、セラミックグリーン層が、この発明に係るセラミック成形体によって与えられる。より具体的には、生のセラミック積層体を作製するため、セラミック原料粉末とバインダ成分と溶剤とを含むセラミックスラリーが用意され、このセラミックスラリーをシート状に成形することによって、セラミックグリーン層を与える複数のセラミックグリーンシートが作製される。特定のセラミックグリーンシート上には内部導体膜３および４がたとえば導電性ペーストの印刷により形成される。その後、これら複数のセラミックグリーンシートが積み重ねられる。
In the raw ceramic laminate described above, the ceramic green layer is provided by the ceramic molded body according to the present invention. More specifically, in order to produce a raw ceramic laminate, a ceramic slurry containing a ceramic raw material powder, a binder component, and a solvent is prepared, and a ceramic green layer is provided by forming the ceramic slurry into a sheet shape. A plurality of ceramic green sheets are produced.
上述したセラミックグリーンシート中のセラミック粒子の充填密度は、前段階のセラミックスラリーの分散性によって左右され、十分な分散条件を実現できないと、セラミックグリーンシート中のセラミック粒子の充填密度は低下する。そのため、分散剤を過剰量添加したりして、分散剤の、セラミック粒子表面への吸着を促進することも考えられるが、その場合、セラミックグリーンシートに占める分散剤の比率が高くなり、その結果、セラミックグリーンシート中のセラミック充填率が低下する。 The packing density of the ceramic particles in the ceramic green sheet described above depends on the dispersibility of the ceramic slurry in the previous stage. If sufficient dispersion conditions cannot be realized, the packing density of the ceramic particles in the ceramic green sheet decreases. For this reason, it may be possible to add an excessive amount of a dispersant to promote the adsorption of the dispersant to the surface of the ceramic particles. In this case, however, the ratio of the dispersant to the ceramic green sheet increases, and as a result The ceramic filling rate in the ceramic green sheet decreases.
また、セラミックグリーンシートにおいては、通常、分子量の大きいバインダ成分がセラミック粒子間に介在し、バインダ成分自身の凝集力でその強度を保っているが、セラミックグリーンシートに占める分散剤の比率が高くなると、セラミックグリーンシート自体の強度が低下し、印刷工程や積層工程などの後工程でのダメージを受けやすく、品質不良へとつながる。 Further, in the ceramic green sheet, a binder component having a large molecular weight is usually interposed between the ceramic particles, and the strength is maintained by the cohesive force of the binder component itself, but when the ratio of the dispersing agent in the ceramic green sheet increases. In addition, the strength of the ceramic green sheet itself is reduced, and the ceramic green sheet itself is easily damaged in subsequent processes such as a printing process and a laminating process, leading to a quality defect.
この発明に係るセラミック成形体によって与えられたセラミックグリーンシートによれば、前述したように、そこに含まれる高分子分散剤の、セラミック粒子表面への吸着率が高く、かつ吸着した分散剤の保持能力が高く、さらに立体障壁としての機能が高いので、セラミックグリーンシート中のセラミック原料粉末の充填密度を高くすることができ、セラミックグリーンシートの密度を高くすることができる。また、セラミックグリーンシート中において分散剤が占める割合を低くすることができるため、セラミックグリーンシートの強度を増すことができ、印刷工程や積層工程などの後工程で受けるダメージの影響を小さくすることができる。また、セラミック原料粉末の凝集が抑制されるため、セラミックグリーンシートの表面を平滑にすることができる。 According to the ceramic green sheet provided by the ceramic molded body according to the present invention, as described above, the polymer dispersant contained therein has a high adsorption rate to the surface of the ceramic particles and retains the adsorbed dispersant. Since the capability is high and 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. In addition, since the proportion of the dispersant in the ceramic green sheet can be reduced, the strength of the ceramic green sheet can be increased, and the influence of damage received in subsequent processes such as the printing process and the laminating process can be reduced. it can. Moreover, since the aggregation of the ceramic raw material powder is suppressed, the surface of the ceramic green sheet can be smoothed.
したがって、このようなセラミックグリーンシートを用いて、セラミック積層体を作製すれば、得られた積層型セラミック電子部品において、ショート不良や絶縁不良などの不良発生率を大幅に低減することができる。 Therefore, if a ceramic laminate is produced using such a ceramic green sheet, the incidence of defects such as short-circuit defects and insulation defects can be greatly reduced in the obtained multilayer ceramic electronic component.
また、前述したように、短時間で分散処理を終了させることができるので、セラミック原料粉末が本来持つ結晶性を維持したまま、グリーンシート化することができる。したがって、積層型セラミック電子部品において、設計どおりの特性を安定して得ることができる。 Further, as described above, since the dispersion treatment can be completed in a short time, a green sheet can be formed while maintaining the crystallinity inherent in the ceramic raw material powder. Therefore, it is possible to stably obtain the designed characteristics in the multilayer ceramic electronic component.
なお、上述したように、セラミック成形体がセラミックグリーンシートである場合に奏される効果は、積層セラミック電子部品を製造するにあたって作製される生のセラミック積層体に備える複数のセラミックグリーン層が、セラミックスラリーを塗布する工程を繰り返すことによって形成される場合にも同様に奏される。 As described above, the effect produced when the ceramic molded body is a ceramic green sheet is that a plurality of ceramic green layers provided in a raw ceramic laminated body produced in manufacturing a multilayer ceramic electronic component are The same effect can be obtained when it is formed by repeating the step of applying the rally.
一般に、セラミック成形体に含まれるセラミック粒子の径が１０ｎｍ〜３００ｎｍというように微粒化されたとき、特に凝集力が増し、均一に分散媒中に分散させることが困難になる。そのため、均一に分散したセラミックスラリーを得ることが困難になり、厚みが１０μｍ以下の欠陥の少ないセラミックグリーンシートを成形することが困難である。 In general, when the diameter of the ceramic particles contained in the ceramic molded body is atomized so as to be 10 nm to 300 nm, especially the cohesive force increases, and it becomes difficult to uniformly disperse in the dispersion medium. Therefore, it becomes difficult to obtain a uniformly dispersed ceramic slurry, and it is difficult to form a ceramic green sheet having a thickness of 10 μm or less and having few defects.
これに対して、この発明に係るセラミック成形体では、セラミック粒子の径が１０ｎｍ〜３００ｎｍと微粒化されても、均一に分散させることができ、厚みが３μｍ以下であっても、欠陥の少ないセラミックグリーンシートを成形することが可能となる。このことから、図１に示すような積層セラミックコンデンサ１において適用されると、セラミック層２の一層の薄層化を進めることができ、大きな静電容量を得ることができる。
On the other hand, in the ceramic molded body according to the present invention, even if the diameter of the ceramic particles is atomized to 10 nm to 300 nm, it can be uniformly dispersed, and even if the thickness is 3 μm or less, the ceramic with few defects A green sheet can be formed. Therefore, when applied to the multilayer
上述したように、セラミック成形体において、セラミック粒子の径が１０ｎｍ〜３００ｎｍと微粒化された場合、高分子分散剤の添加量は、セラミック粒子１００重量部に対して、０．１〜１０重量部であることが好ましい。 As described above, in the ceramic molded body, when the diameter of the ceramic particles is atomized to 10 nm to 300 nm, the addition amount of the polymer dispersant is 0.1 to 10 parts by weight with respect to 100 parts by weight of the ceramic particles. It is preferable that
なお、この発明に係るセラミック成形体は、上述したセラミックグリーンシートあるいは生のセラミック積層体におけるセラミックグリーン層の他、硬化型バインダ成分を含むセラミックスラリーを鋳型の中に充填し、バインダ成分を硬化させることにより、所定の形状が付与されたものをも含む。 In addition, the ceramic molded body according to the present invention is filled with a ceramic slurry containing a curable binder component in addition to the ceramic green sheet or the ceramic green layer in the raw ceramic laminate, and the binder component is cured. By this, the thing to which the predetermined shape was given is also included.
以下に、この発明に基づいて実施した実験例について説明する。 Below, the experiment example implemented based on this invention is demonstrated.
［実験例１］
高分子分散剤として、以下のように作製したものを用いた。[Experimental Example 1]
As the polymer dispersant, one prepared as follows was used.
還流管、攪拌装置、温度計および窒素導入管を取り付けたセパラブルフラスコに、メタクリル酸ステアリル（新中村化学社製、ＮＫ−エステル Ｓ）を２．２５ｇ、メトキシポリエチレングリコール（９）メタクリレート（新中村化学社製、ＮＫ−エステル Ｍ−９０Ｇ、エチレンオキサイドの平均付加モル数 ９）を１０．５ｇ、メタクリル酸（和光純薬工業社製試薬）を２．２５ｇ、およびトルエン（和光純薬工業社製試薬）を６．０ｇそれぞれ仕込み、窒素置換し、６５℃に加熱した。 In a separable flask equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, 2.25 g of stearyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK-ester S), methoxypolyethylene glycol (9) methacrylate (Shin-Nakamura) 10.5 g of NK-ester M-90G, average addition mole number of ethylene oxide 9), 2.25 g of methacrylic acid (a reagent manufactured by Wako Pure Chemical Industries), and toluene (manufactured by Wako Pure Chemical Industries, Ltd.) Reagent) was charged in an amount of 6.0 g, purged with nitrogen and heated to 65 ° C.
槽内が６５℃に到達後、２，２’−アゾビス（２，４−ジメチルバレロニトリル）（Ｖ−６５Ｂ：和光純薬工業社製）を０．４５ｇおよびトルエンを２．５ｇ含む混合物を添加した。 After the tank reached 65 ° C., a mixture containing 0.45 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65B: Wako Pure Chemical Industries) and 2.5 g of toluene was added. did.
その後、メタクリル酸ステアリルを２０．２５ｇ、メトキシポリエチレングリコール（９）メタクリレートを９４．５ｇ、メタクリル酸を２０．２５ｇ、トルエンを９０ｇ、およびＶ−６５Ｂを４．０５ｇ含む混合液を、３時間かけて滴下した。 Thereafter, a mixed solution containing 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 4.05 g of V-65B was taken over 3 hours. It was dripped.
６５℃で３時間攪拌後、冷却した。濃度調整のために、トルエンを添加し、目的とする高分子分散剤のトルエン溶液を得た。この溶液の不揮発分は３９．４重量％であり、高分子分散剤の重量平均分子量は４４２００であった。 The mixture was stirred at 65 ° C. for 3 hours and then cooled. To adjust the concentration, toluene was added to obtain a toluene solution of the target polymer dispersant. The nonvolatile content of this solution was 39.4% by weight, and the weight average molecular weight of the polymer dispersant was 44200.
平均粒径０．３μｍの市販のチタン酸バリウム粉末を１００重量部、上記高分子分散剤を有効分で０．２重量部（チタン酸バリウム粉末の表面積あたり分散剤が１．６ｍｇ／ｍ２）、バインダ（ポリビニルブチラールバインダ）を１０重量部、可塑剤（ジオクチルフタレート）を２重量部、溶剤としてトルエンを７０重量部、エタノールを７０重量部の各割合で配合した。100 parts by weight of a commercially available barium titanate powder having an average particle size of 0.3 μm, and 0.2 parts by weight of the above polymer dispersant in an effective amount (the dispersant is 1.6 mg / m 2 per surface area of the barium titanate powder) , 10 parts by weight of a binder (polyvinyl butyral binder), 2 parts by weight of a plasticizer (dioctyl phthalate), 70 parts by weight of toluene as a solvent, and 70 parts by weight of ethanol were blended.
上記の配合物に直径１ｍｍのジルコニア製の玉石５００重量部を添加し、後述する所定の処理時間をもって、ボールミルにて混合・解砕処理して、実施例に係るセラミックグリーンシート製造用のセラミックスラリーを得た。 A ceramic slurry for producing a ceramic green sheet according to the example is added to the above-mentioned composition by adding 500 parts by weight of cobblestone made of zirconia having a diameter of 1 mm and mixing and crushing with a ball mill for a predetermined processing time to be described later. Got.
他方、上記高分子分散剤をオレイン酸系の分散剤に置き換えたこと、およびボールミルによる処理時間を後述するように変更したことを除いて、同様の組成および同様の操作により、比較例に係るセラミックグリーンシート製造用のセラミックスラリーを得た。 On the other hand, the ceramic according to the comparative example was obtained by the same composition and the same operation except that the polymer dispersant was replaced with an oleic acid dispersant and the treatment time by the ball mill was changed as described later. A ceramic slurry for green sheet production was obtained.
上述したボールミルによる処理時間は次のとおりとした。上述した実施例および比較例の各々に係るセラミックスラリーについて、最適な分散状態を得るために必要なボールミル処理時間を以下のようにして求めた。すなわち、ボールミルによる処理の所定時間経過ごとに、スラリー粒度分布計にて粒度を測定し、各セラミックスラリー中でのセラミック粒子の平均粒径（Ｄ５０）を求めた。その結果が図２に示されている。そして、各セラミックスラリー中でのセラミック粒子の平均粒径（Ｄ５０）が変化しなくなる最短の時間を求めた。 The processing time by the above-mentioned ball mill was as follows. For the ceramic slurries according to each of the above-described examples and comparative examples, the ball mill treatment time required to obtain an optimal dispersion state was determined as follows. That is, the particle size was measured with a slurry particle size distribution meter every predetermined time of the treatment by the ball mill, and the average particle size (D50) of the ceramic particles in each ceramic slurry was obtained. The result is shown in FIG. And the shortest time when the average particle diameter (D50) of the ceramic particle in each ceramic slurry did not change was calculated | required.
図２に示すように、実施例に係るセラミックスラリーでは、セラミック粒子の一次粒径にまで平均粒径（Ｄ５０）が低下しており、また、約５時間経過後から平均粒径（Ｄ５０）が一定値を示した。 As shown in FIG. 2, in the ceramic slurry according to the example, the average particle size (D50) is reduced to the primary particle size of the ceramic particles, and the average particle size (D50) is about 5 hours later. A constant value was shown.
他方、比較例に係るセラミックスラリーでは、２０時間を経過しても、平均粒径（Ｄ５０）が一定値に収束せず、また、セラミック粒子の一次粒径にまで到達しなかった。 On the other hand, in the ceramic slurry according to the comparative example, even after 20 hours, the average particle size (D50) did not converge to a constant value, and did not reach the primary particle size of the ceramic particles.
上記評価結果より、実施例に係るセラミックスラリーを得るにあたっては、ボールミル処理時間を５時間に設定し、比較例に係るセラミックスラリーを得るにあたっては、ボールミル処理時間を２０時間に設定した。 From the above evaluation results, when obtaining the ceramic slurry according to the example, the ball mill treatment time was set to 5 hours, and when obtaining the ceramic slurry according to the comparative example, the ball mill treatment time was set to 20 hours.
次に、上記のようにして得られた実施例および比較例に係るセラミックスラリーに対して、ドクターブレード法を適用して、シート厚み１μｍ、５μｍおよび１０μｍの各々のセラミックグリーンシートを成形した。 Next, a doctor blade method was applied to the ceramic slurries according to Examples and Comparative Examples obtained as described above to form ceramic green sheets having sheet thicknesses of 1 μm, 5 μm, and 10 μm.
このようにして得られたセラミックグリーンシートの表面粗さ（Ｒａ）を原子間力顕微鏡で測定し、さらに、セラミックグリーンシートの密度を定量化するために、セラミックグリーンシートの密度比（実測密度と理論密度との比）を求めた。また、セラミックグリーンシートの破断強度を測定した。 In order to measure the surface roughness (Ra) of the ceramic green sheet thus obtained with an atomic force microscope, and to further quantify the density of the ceramic green sheet, the density ratio of the ceramic green sheet (measured density and Ratio to theoretical density). Moreover, the breaking strength of the ceramic green sheet was measured.
他方、上述したセラミックグリーンシートを用いて、周知の方法により、試料となる積層セラミックコンデンサを作製した。そして、得られた積層セラミックコンデンサについて、ショート発生率、および静電容量の温度特性を評価した。 On the other hand, a multilayer ceramic capacitor serving as a sample was produced by a known method using the ceramic green sheet described above. The resulting multilayer ceramic capacitor was evaluated for short-circuit occurrence rate and temperature characteristics of capacitance.
これらの評価結果が表１に示されている。 These evaluation results are shown in Table 1.
表１からわかるように、実施例によれば、比較例に比べて、セラミックグリーンシートの表面粗さおよび密度比がともに良好である。また、実施例によれば、比較例に比べて、破断強度も高い。この破断強度については、特に、シート厚みが薄い領域で、実施例と比較例との間での差が顕著に現れている。 As can be seen from Table 1, according to the example, both the surface roughness and the density ratio of the ceramic green sheet are better than those of the comparative example. Further, according to the examples, the breaking strength is higher than that of the comparative example. About this breaking strength, the difference between an Example and a comparative example has appeared notably in the area | region where sheet | seat thickness is thin.
さらに、積層セラミックコンデンサにおいては、実施例によれば、比較例に比べて、ショート発生率が改善されている。ここで、比較例では、シート厚みが１０μｍ以下になると、ショート発生率が急増するが、実施例では、ショート発生率は極めて低く、セラミック層の薄層化と不良率低減とが両立していることがわかる。 Furthermore, in the multilayer ceramic capacitor, according to the example, the short-circuit occurrence rate is improved as compared with the comparative example. Here, in the comparative example, when the sheet thickness is 10 μm or less, the short-circuit occurrence rate increases rapidly. However, in the example, the short-circuit occurrence rate is extremely low, and both the thinning of the ceramic layer and the reduction of the defect rate are compatible. I understand that.
また、静電容量の温度特性を見ると、実施例では、Ｂ特性（−２５〜＋８５℃の温度範囲で、静電容量変化率が±１０％以内）を満足しているが、比較例では、Ｘ５Ｒ特性（−５５〜８５℃の温度範囲で、静電容量変化率が±１５％以内）までしか満足できていない。これは、比較例では、チタン酸バリウム粉末の分散効率が悪く、ボールミル処理時間が長時間になったため、セラミック自体の結晶性が損なわれ、特性が悪化したものと推測される。 Further, looking at the temperature characteristics of the capacitance, in the example, the B characteristic (capacitance change rate within ± 10% within the temperature range of −25 to + 85 ° C.) is satisfied, but in the comparative example, , X5R characteristics (capacitance change rate within ± 15% within a temperature range of −55 to 85 ° C.) can only be satisfied. This is presumed that, in the comparative example, the dispersion efficiency of the barium titanate powder was poor and the ball mill treatment time was long, so that the crystallinity of the ceramic itself was impaired and the characteristics deteriorated.
［実験例２］
実験例２では、チタン酸バリウム粉末の平均粒径を５０ｎｍと微粒化し、高分子分散剤の含有量を有効分で４．０重量部（チタン酸バリウム粉末の表面積あたり分散剤が１．６ｍｇ／ｍ２）と変更したことを除いて、実験例１と同様の条件および同様の操作によって、実施例に係るセラミックグリーンシートおよび積層セラミックコンデンサを作製した。[Experiment 2]
In Experimental Example 2, the average particle diameter of the barium titanate powder was atomized to 50 nm, and the content of the polymer dispersant was 4.0 parts by weight (the dispersant was 1.6 mg / per surface area of the barium titanate powder). A ceramic green sheet and a multilayer ceramic capacitor according to the example were manufactured under the same conditions and the same operation as in Experimental Example 1 except that the value was changed to m 2 ).
実験例２においても、上記高分子分散剤をオレイン酸系の分散剤に置き換えたこと、およびボールミルによる処理時間を変更したことを除いて、同様の組成および同様の操作により、比較例に係るセラミックグリーンシートおよび積層セラミックコンデンサを作製した。 Also in Experimental Example 2, the ceramic according to the comparative example was obtained by the same composition and the same operation except that the polymer dispersant was replaced with an oleic acid-based dispersant and the treatment time by the ball mill was changed. Green sheets and multilayer ceramic capacitors were produced.
また、実験例１の場合と同様にして、評価を行なった。その結果が表２に示されている。 The evaluation was performed in the same manner as in Experimental Example 1. The results are shown in Table 2.
実験例２においても、実施例によれば、実験例１の場合と同様、比較例に比べて、セラミックグリーンシートの表面粗さ、密度比および破断強度、ならびに積層セラミックコンデンサのショート発生率および静電容量の温度特性に関して、より良好な結果が得られている。 Also in Experimental Example 2, according to the example, similar to the case of Experimental Example 1, compared with the comparative example, the surface roughness, density ratio and breaking strength of the ceramic green sheet, and the occurrence rate of short and static of the multilayer ceramic capacitor Better results have been obtained regarding the temperature characteristics of the capacitance.
また、この実験例２における実施例によれば、実験例１における実施例に比べて、セラミック粒子径が小さくなっているので、表面粗さ、密度比、破断強度、ショート発生率に関して、より良好な結果が得られている。 Further, according to the example in this experimental example 2, since the ceramic particle diameter is smaller than that in the example in experimental example 1, the surface roughness, the density ratio, the breaking strength, and the short-circuit occurrence rate are better. Results are obtained.
他方、実験例２における比較例では、実験例１における比較例に比べて、表面粗さが向上しているが、密度比および破断強度については逆に悪化しており、ショート発生率も悪化する傾向が見られる。 On the other hand, in the comparative example in Experimental Example 2, the surface roughness is improved as compared with the comparative example in Experimental Example 1, but the density ratio and the breaking strength are worsened on the contrary, and the occurrence rate of short circuit is also worsened. There is a trend.
以上の結果は、この発明によれば、より細かい粒径のセラミック粒子への適応が可能となったことを示している。 The above results indicate that the present invention can be applied to finer ceramic particles.
［実験例３］
実験例３では、チタン酸バリウム粉末の平均粒径を１０ｎｍとさらに微粒化し、高分子分散剤の含有量を有効分で４．０重量部（チタン酸バリウム粉末の表面積あたり分散剤が０．４ｍｇ／ｍ２）と変更したことを除いて、実験例１と同様の条件および同様の操作によって、実施例に係るセラミックグリーンシートおよび積層セラミックコンデンサを作製した。[Experiment 3]
In Experimental Example 3, the average particle size of the barium titanate powder was further refined to 10 nm, and the content of the polymer dispersant was 4.0 parts by weight (the dispersant was 0.4 mg per surface area of the barium titanate powder). Except for the change to / m 2 ), a ceramic green sheet and a multilayer ceramic capacitor according to the example were manufactured under the same conditions and the same operation as in Experimental Example 1.
実験例３においても、上記高分子分散剤をオレイン酸系の分散剤に置き換えたこと、およびボールミルによる処理時間を変更したことを除いて、同様の組成および同様の操作により、比較例に係るセラミックグリーンシートおよび積層セラミックコンデンサを作製した。 Also in Experimental Example 3, the ceramic according to the comparative example was obtained by the same composition and the same operation except that the polymer dispersant was replaced with an oleic acid-based dispersant and the treatment time by the ball mill was changed. Green sheets and multilayer ceramic capacitors were produced.
また、実験例１の場合と同様にして、評価を行なった。その結果が表３に示されている。 The evaluation was performed in the same manner as in Experimental Example 1. The results are shown in Table 3.
実施例によれば、実験例１の場合と同様、比較例に比べて、セラミックグリーンシートの表面粗さ、密度比および破断強度、ならびに積層セラミックコンデンサのショート発生率および静電容量の温度特性に関して、より良好な結果が得られている。 According to the example, as in the case of Experimental Example 1, compared with the comparative example, the surface roughness, density ratio and breaking strength of the ceramic green sheet, and the short-circuit occurrence rate of the multilayer ceramic capacitor and the temperature characteristics of the capacitance Better results have been obtained.
また、この実験例３における実施例についても、実験例１における実施例に比べて、セラミック粒子径が小さくなっているので、表面粗さ、密度比、破断強度、ショート発生率に関して、より良好な結果が得られている。 Moreover, since the ceramic particle diameter is smaller in the example in the experimental example 3 than in the example in the experimental example 1, the surface roughness, the density ratio, the breaking strength, and the short-circuit occurrence rate are better. The result is obtained.
他方、実験例３における比較例では、実験例１における比較例に比べて、表面粗さが向上しているが、密度比および破断強度については逆に悪化しており、ショート発生率も悪化する傾向が見られる。 On the other hand, in the comparative example in Experimental Example 3, the surface roughness is improved as compared with the comparative example in Experimental Example 1, but the density ratio and breaking strength are worsened on the contrary, and the occurrence rate of short circuit is also worsened. There is a trend.
以上の結果は、この発明によれば、より細かい粒径、実験例２に比べてもさらに細かい粒径のセラミック粒子への適応が可能となったことを示している。 The above results show that, according to the present invention, it is possible to adapt to ceramic particles having a finer particle diameter, even smaller than that of Experimental Example 2.
［実験例４］
実験例４では、チタン酸バリウム粉末として、平均粒径が１０ｎｍ、５０ｎｍおよび３００ｎｍのものをそれぞれ用いながら、高分子分散剤の添加量を有効分で０．０５〜２０重量部の範囲で変えたことを除いて、実験例１と同様の条件および同様の操作によって、セラミックグリーンシートおよび積層セラミックコンデンサを作製した。[Experimental Example 4]
In Experimental Example 4, the barium titanate powder having an average particle size of 10 nm, 50 nm, and 300 nm was used, and the addition amount of the polymer dispersant was changed in the range of 0.05 to 20 parts by weight in an effective amount. Except for the above, a ceramic green sheet and a multilayer ceramic capacitor were produced under the same conditions and the same operation as in Experimental Example 1.
また、実験例１の場合と同様にして、静電容量の温度特性以外の評価を行なった。その結果が表４ないし表６に示されている。ここで、表４は、チタン酸バリウム粉末の平均粒径が３００ｎｍの場合を示し、表５は、チタン酸バリウム粉末の平均粒径が５０ｎｍの場合を示し、表６は、チタン酸バリウム粉末の平均粒径が１０ｎｍの場合を示している。 Further, in the same manner as in Experimental Example 1, evaluations other than the temperature characteristics of the capacitance were performed. The results are shown in Tables 4-6. 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 of the barium titanate powder. The case where the average particle diameter is 10 nm is shown.
表４ないし表６からわかるように、セラミック粒子の平均粒径によって、高分子分散剤の最適な添加量は異なるが、セラミック粒子の平均粒径が１０ｎｍ〜３００ｎｍの範囲にある場合、高分子分散剤の添加量としては、０．１〜１０重量部に選ぶことが好ましく、０．２〜５重量部に選ぶことがより好ましい。 As can be seen from Tables 4 to 6, the optimum addition amount of the polymer dispersant varies depending on the average particle size of the ceramic particles, but when the average particle size of the ceramic particles is in the range of 10 nm to 300 nm, the polymer dispersion The addition amount of the agent is preferably selected from 0.1 to 10 parts by weight, and more preferably from 0.2 to 5 parts by weight.
以上、実験例１ないし４では、高分子分散剤として、前述したように製造された特定のものを用いたが、これに限らず、前述したように、一般式（１）で示される構成単位Ａを全構成単位中５〜４５重量％、一般式（２）で示される構成単位Ｂを全構成単位中５０〜９０重量％、および、一般式（３）で示される構成単位Ｃを構成単位Ｂに対する重量比（構成単位Ｃ／構成単位Ｂ）で０．０５〜０．７含有する、共重合体からなる高分子分散剤であれば、いずれの組成のものを用いても、良好な結果が得られる。このことを確認するため、以下の実験を行なった。 As described above, in Experimental Examples 1 to 4, the specific polymer manufactured as described above was used as the polymer dispersant. However, the present invention is not limited to this, and as described above, the structural unit represented by the general formula (1) is used. A is 5 to 45% by weight in all the structural units, structural unit B represented by the general formula (2) is 50 to 90% by weight in all the structural units, and structural unit C represented by the general formula (3) is the structural unit. Good results can be obtained with any composition as long as it is a polymer dispersing agent comprising a copolymer and having a weight ratio to B (constituent unit C / constituent unit B) of 0.05 to 0.7. Is obtained. In order to confirm this, the following experiment was conducted.
［実験例５］
下の表７に示す原料および仕込み量を用いて、実験例１において用意した高分子分散剤の場合と同様の方法にて、いくつかの種類の高分子分散剤を製造した。なお、表７に示した高分子分散剤ＤＡ１〜ＤＡ１４のうち、高分子分散剤ＤＡ１は、実験例１ないし４において用いた高分子分散剤である。また、高分子分散剤ＤＡ１２〜ＤＡ１４は、この発明の範囲外のものである。[Experimental Example 5]
Several types of polymer dispersants were produced in the same manner as in the case of the polymer dispersant prepared in Experimental Example 1 using the raw materials and preparation amounts shown in Table 7 below. Of the polymer dispersants DA1 to DA14 shown in Table 7, the polymer dispersant DA1 is the 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において、「ＭＭＡ」はメタクリル酸、「ＰＥＧＭＡ」はメトキシポリエチレングリコールメタクリレート、「ＳＭＡ」はステアリルメタクリレート、「ＭＭＡ」はメチルメタクリレート、「Ｓｔ」はスチレン、「ＩＰＡ」はイソプロパノール、「ＭＰＤ」は３メルカプト１，２プロパンジオールである。また、「ＰＥＧＭＡ」において、「ＰＥＧＭＡ（４）」はエチレンオキサイドの平均付加モル数が４のメトキシポリエチレングリコールメタクリレートであり、「ＰＥＧＭＡ（９）」はエチレンオキサイドの平均付加モル数が９のメトキシポリエチレングリコールメタクリレートであり、「ＰＥＧＭＡ（２３）」はエチレンオキサイドの平均付加モル数が２３のメトキシポリエチレングリコールメタクリレートである。
In Table 7, “MMA” is methacrylic acid, “PEGMA” is methoxypolyethylene glycol methacrylate, “SMA” is stearyl methacrylate, “MMA” is methyl methacrylate, “St” is styrene, “IPA” is isopropanol, and “MPD” is 3
表７において、各高分子分散剤の重量平均分子量および不揮発分も示されている。 In Table 7, the weight average molecular weight and nonvolatile content of each polymer dispersant are also shown.
他方、平均粒径２００ｎｍ（ＢＥＴ比表面積５ｍ２／ｇ）のチタン酸バリウム粉末および平均粒径１００ｎｍ（ＢＥＴ比表面積１０ｍ２／ｇ）のチタン酸バリウム粉末を用意した。On the other hand, barium titanate powder having an average particle size of 200 nm (BET specific surface area of 5 m 2 / g) and barium titanate powder having an average particle size of 100 nm (BET specific surface area of 10 m 2 / g) were prepared.
次に、上記高分子分散剤および各チタン酸バリウム粉末を用いて、表８に示す試料１〜１８の各々に係るセラミックスラリーを以下のように作製した。
Next, using the polymer dispersant and each barium titanate powder, ceramic slurries according to each of
３６ｇのチタン酸バリウム粉末および０．３ｇ（有効分）の高分子分散剤を、直径１ｍｍのジルコニア製の玉石１５０ｇと一緒に、２５０ｍＬの容器に入れ、トルエン／エタノール＝４８／５２（容積比）の混合液を加えて、チタン酸バリウムの固形分濃度が３０％になるように調整した。次いで、容器をペイントシェーカー（浅田鉄工社製）で１時間振とうし、解砕・分散させ、試料１〜１８の各々に係るセラミックスラリーを得た。
36 g of barium titanate powder and 0.3 g (effective amount) of a polymer dispersant are placed in a 250 mL container together with 150 g of zirconia cobblestone having a diameter of 1 mm, and toluene / ethanol = 48/52 (volume ratio). Was added to adjust the solid content concentration of barium titanate to 30%. Next, the container was shaken with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for 1 hour, crushed and dispersed, and ceramic slurries according to each of
次に、セラミックスラリー中のチタン酸バリウム粒子の粒径を、光子相関法（動的光散乱法）の原理に基づくシスメックス社製の粒度分布測定機「ゼータサイザーナノＺＳ」を用いて測定し、Ｄ５０およびＤ９０をそれぞれ求めるとともに、Ｄ９０／Ｄ５０の比を算出した。Ｄ５０の値が、用いたチタン酸バリウム粉末の平均粒径により近いほど、また、Ｄ９０／Ｄ５０の比がより小さいほど、すなわち粒径分布がより狭いほど、分散性が優れていることを示している。 Next, the particle size of the barium titanate particles in the ceramic slurry was measured using a particle size distribution measuring instrument “Zetasizer Nano ZS” manufactured by Sysmex Corporation based on the principle of the photon correlation method (dynamic light scattering method), D50 and D90 were determined, respectively, and the ratio D90 / D50 was calculated. It shows that the closer the D50 value is to the average particle size of the barium titanate powder used and the smaller the D90 / D50 ratio, that is, the narrower the particle size distribution, the better the dispersibility. Yes.
上記の結果が、以下の表８に示されている。 The above results are shown in Table 8 below.
表８に示すように、高分子分散剤ＤＡ１〜ＤＡ１１を用いた試料１〜１５に係るセラミックスラリーでは、いずれも、Ｄ５０の値がチタン酸バリウムの平均粒径に近く、Ｄ９０／Ｄ５０の比も２．１以下である。
As shown in Table 8, in each of the ceramic slurries according to
これに対して、Ｃ／Ｂ重量比が０．０５〜０．７の範囲から外れている高分子分散剤ＤＡ１２〜ＤＡ１４を用いた試料１６および１７に係るセラミックスラリーでは、Ｄ５０の値は、チタン酸バリウムの平均粒径に近いものの、上記試料１〜１５に比べるとより大きく、また、Ｄ９０／Ｄ５０の比については２．９以上と大きい。
On the other hand, in the ceramic slurry according to
また、構成単位Ａを含有しない高分子分散剤ＤＡ１４を用いた試料１８に係るセラミックスラリーでは、Ｄ５０の値がチタン酸バリウムの平均粒径よりかなり大きい。
Further, in the ceramic slurry according to the
以上のことから、試料１〜１５に係るセラミックスラリーの分散性は、試料１６〜１８に係るセラミックスラリーの分散性より優れていることがわかる。よって、実験例１ないし４において用いた高分子分散剤に限らず、前述したように、一般式（１）で示される構成単位Ａを全構成単位中５〜４５重量％、一般式（２）で示される構成単位Ｂを全構成単位中５０〜９０重量％、および、一般式（３）で示される構成単位Ｃを構成単位Ｂに対する重量比（構成単位Ｃ／構成単位Ｂ）で０．０５〜０．７含有する、共重合体からなる高分子分散剤であれば、いずれの組成のものを用いても、セラミックグリーンシートについての表面粗さ、密度比および破断強度、ならびに積層セラミックコンデンサについてのショート発生率等について良好な結果が得られることが理解される。 From the above, it can be seen that the dispersibility of the ceramic slurry according to Samples 1-15 is superior to the dispersibility of the ceramic slurry according to Samples 16-18. Therefore, not only the polymer dispersant used in Experimental Examples 1 to 4, but as described above, the structural unit A represented by the general formula (1) is 5 to 45% by weight in the total structural units, and the general formula (2). The structural unit B is represented by 50 to 90% by weight in the total structural units, and the structural unit C represented by the general formula (3) is 0.05 by weight ratio (structural unit C / structural unit B) to the structural unit B. As long as it is a polymer dispersant made of a copolymer containing ~ 0.7, the surface roughness, density ratio and breaking strength of the ceramic green sheet, and the multilayer ceramic capacitor can be used regardless of the composition. It is understood that good results can be obtained for the occurrence rate of short circuit.
１ 積層セラミックコンデンサ
２ セラミック層
３ 内部導体膜
５ セラミック積層体DESCRIPTION OF
Claims (6)
前記セラミック原料粉末を構成するセラミック粒子の表面が分散剤によって覆われていて、
前記分散剤は、下記一般式（１）で示される構成単位Ａを全構成単位中５〜４５重量％、下記一般式（２）で示される構成単位Ｂを全構成単位中５０〜９０重量％、および、下記一般式（３）で示される構成単位Ｃを構成単位Ｂに対する重量比（構成単位Ｃ／構成単位Ｂ）で０．０５〜０．７含有する、共重合体からなる高分子分散剤を含む、セラミック成形体。
上記式（３）において、Ｒ９、Ｒ１０およびＲ１１は同一または異なり、水素原子または炭素数１〜２のアルキル基を示し、Ｘ２は酸素原子またはＮＨを示し、Ｒ１２およびＲ１３は炭素数１〜３０の直鎖、分岐鎖もしくは環状のアルキル基もしくはアルケニル基またはアリール基を示す。A ceramic molded body obtained by giving a predetermined shape to a ceramic slurry containing a ceramic raw material powder, a binder component and a solvent,
The surface of the ceramic particles constituting the ceramic raw material powder is covered with a dispersant,
In the dispersant, the structural unit A represented by the following general formula (1) is 5 to 45% by weight in all the structural units, and the structural unit B represented by the following general formula (2) is 50 to 90% by weight in all the structural units. And a polymer dispersion comprising a copolymer containing 0.05 to 0.7 of the structural unit C represented by the following general formula (3) in a weight ratio to the structural unit B (structural unit C / structural unit B) Ceramic molded body containing an agent.
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 linear, branched or cyclic alkyl group, alkenyl group or aryl group having 1 to 30 carbon atoms is shown.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010526674A JP5267565B2 (en) | 2008-08-27 | 2009-08-21 | Method for manufacturing ceramic molded body and multilayer ceramic electronic component |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008217540 | 2008-08-27 | ||
| JP2008217540 | 2008-08-27 | ||
| PCT/JP2009/064614 WO2010024188A1 (en) | 2008-08-27 | 2009-08-21 | Molded ceramic and process for producing multilayered ceramic electronic part |
| JP2010526674A JP5267565B2 (en) | 2008-08-27 | 2009-08-21 | Method for manufacturing ceramic molded body and multilayer ceramic electronic component |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2010024188A1 true JPWO2010024188A1 (en) | 2012-01-26 |
| JP5267565B2 JP5267565B2 (en) | 2013-08-21 |
Family
ID=41721356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010526674A Active JP5267565B2 (en) | 2008-08-27 | 2009-08-21 | Method for manufacturing ceramic molded body and multilayer ceramic electronic component |
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 |
| JP7470780B2 (en) | 2020-03-30 | 2024-04-18 | 富士フイルム株式会社 | 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 CN CN2009801319647A patent/CN102123968A/en active Pending
- 2009-08-21 JP JP2010526674A patent/JP5267565B2/en active Active
- 2009-08-21 WO PCT/JP2009/064614 patent/WO2010024188A1/en active Application Filing
- 2009-08-21 TW TW98128253A patent/TWI432397B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010024188A1 (en) | 2010-03-04 |
| JP5267565B2 (en) | 2013-08-21 |
| TWI432397B (en) | 2014-04-01 |
| TW201010963A (en) | 2010-03-16 |
| CN102123968A (en) | 2011-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5267565B2 (en) | Method for manufacturing ceramic molded body and multilayer ceramic electronic component | |
| KR101275426B1 (en) | Conductive paste composition for internal electrode, multilayer ceramic capacitor and method of manufacturing the same | |
| TW510848B (en) | Method for producing ceramic slurry, method for forming ceramic green sheet, and method for fabricating monolithic ceramic electronic component | |
| JP2003242835A (en) | Conductive paste for photogravure printing and its producing method as well as laminated ceramic electronic component | |
| JP4403920B2 (en) | Method for producing release layer paste and method for producing multilayer electronic component | |
| TW202120570A (en) | Binder composition for forming green sheet, slurry for forming green sheet, green sheet and method for producing same, and device and method for producing same | |
| WO2015040924A1 (en) | Ceramic molded body, and method for producing stacked ceramic electronic component | |
| US20040092652A1 (en) | Water-soluble acrylic binder, method for producing the same, ceramic slurry composition, method for producing the same, monolithic ceramic electronic part and method for manufacturing the same | |
| TWI297341B (en) | A copolymer which is used as a dispersing agent for titanate-based ceramic colloids | |
| US20120048452A1 (en) | Method of manufacturing ceramic paste for multilayer ceramic electronic component and method of manufacturing multilayer ceramic electronic component having the same | |
| JP6809280B2 (en) | Method of manufacturing conductive paste | |
| JP7180282B2 (en) | Metal oxide nanoparticle dispersion for firing and method for producing sintered film | |
| CN107452435B (en) | Paste for forming conductor | |
| WO2005087688A1 (en) | Dielectric paste for multilayer ceramic electronic component and method for producing multilayer unit for multilayer ceramic electronic component | |
| JP2006080496A (en) | Paste for releasable layer, and method of manufacturing laminated electronic component | |
| KR100593888B1 (en) | Method for Manufacturing a Hybrid Sol for Producing a Laminate of High-Capacity Multilayer Ceramic Capacitor and the Hybrid Sol therefrom | |
| JP7164410B2 (en) | Paste composition for internal electrode of laminated ceramic part and laminated ceramic part | |
| JP4890815B2 (en) | Method for producing electrode for electric double layer capacitor and method for producing separator for electric double layer capacitor | |
| JP4817633B2 (en) | Method for preparing ceramic slurry and method for producing ceramic | |
| JP2005243333A (en) | Conductive paste | |
| JP5459951B2 (en) | Method for producing ceramic slurry | |
| JP2024514319A (en) | Electrode composition for electric spray | |
| TWI434860B (en) | Synthesis and Application of Novel Amphoteric Monomers, Their Synthesis, and Their Derivative Amphoteric Copolymer and Copolymer | |
| TW202411411A (en) | Carboxy group-containing polymer dispersant, electroconductive paste, electronic component, and laminated ceramic capacitor | |
| JP2023048700A (en) | Ceramic powder and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121204 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130125 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130409 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130422 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5267565 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |