WO2011010663A1 - Particles coated with cuprous oxide, method for producing same, and antifouling coating material containing the particles coated with cuprous oxide - Google Patents
Particles coated with cuprous oxide, method for producing same, and antifouling coating material containing the particles coated with cuprous oxide Download PDFInfo
- Publication number
- WO2011010663A1 WO2011010663A1 PCT/JP2010/062247 JP2010062247W WO2011010663A1 WO 2011010663 A1 WO2011010663 A1 WO 2011010663A1 JP 2010062247 W JP2010062247 W JP 2010062247W WO 2011010663 A1 WO2011010663 A1 WO 2011010663A1
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- WO
- WIPO (PCT)
- Prior art keywords
- cuprous oxide
- core material
- coated particles
- surface treatment
- particles
- Prior art date
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 186
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 186
- 239000002245 particle Substances 0.000 title claims abstract description 155
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000011248 coating agent Substances 0.000 title abstract description 7
- 238000000576 coating method Methods 0.000 title abstract description 7
- 239000000463 material Substances 0.000 title abstract description 7
- 239000011162 core material Substances 0.000 claims abstract description 89
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 47
- 238000004070 electrodeposition Methods 0.000 claims abstract description 46
- 239000007864 aqueous solution Substances 0.000 claims description 65
- 238000004381 surface treatment Methods 0.000 claims description 57
- 239000003973 paint Substances 0.000 claims description 32
- 239000010949 copper Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000000049 pigment Substances 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 150000002940 palladium Chemical class 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 3
- 150000002484 inorganic compounds Chemical class 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 21
- 238000003860 storage Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 25
- 239000000047 product Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 238000005406 washing Methods 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 230000005484 gravity Effects 0.000 description 16
- -1 chlorine ions Chemical class 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 235000011187 glycerol Nutrition 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- JDVPAQRYDGZAFW-UHFFFAOYSA-N [methyl(dipropyl)silyl] prop-2-enoate Chemical compound C(C=C)(=O)O[Si](CCC)(CCC)C JDVPAQRYDGZAFW-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
- 229960002799 stannous fluoride Drugs 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
Definitions
- cuprous oxide layer it is preferably 50 or more, more preferably 60 or more cuprous oxide particles per 100 cuprous oxide particles to be observed. If is octahedral, the above-described advantageous effects are exhibited.
- the octahedral cuprous oxide particles may be stacked regularly to form a layer, or randomly stacked to form a layer.
- the shape of the core material can also be appropriately selected according to the specific use of the cuprous oxide-coated particles.
- a spherical shape, a cubic shape, a plate shape, a lump shape, or the like can be used.
- a satisfactory effect can be obtained by using a spherical core material.
- the core material may be solid or hollow.
- metallic copper is used as the anode as described above.
- a metallic copper plate may be usually used.
- the purity of metallic copper should just be 99% or more.
- plate-like metallic copper or stainless steel can be used as the cathode.
- the surface treatment of the core material is performed by adding the surface treatment product of the core material to the aqueous electrolyte solution and stirring the aqueous electrolyte solution to disperse the surface treatment of the core material. Electrodeposit cuprous oxide on the surface of the object.
- the thickness of the cuprous oxide layer formed on the surface of the core material that is, the coating amount of the cuprous oxide can be adjusted by the electrodeposition time.
- an electrodeposition time of about 10 minutes to 4 hours. Is preferred.
- the cuprous oxide-coated particles In the water washing step, it is preferable to wash the cuprous oxide-coated particles with washing water containing an antioxidant from the viewpoint of preventing the cuprous oxide from being oxidized.
- an antioxidant glycerol, saccharides, etc. can be used, for example.
- the concentration of the antioxidant in the washing water is preferably 0.3 to 60 g / L, particularly preferably 0.5 to 40 g / L.
- the cuprous oxide-coated particles thus obtained are particularly suitably used as a pigment for antifouling paints, for example.
- This antifouling paint is used for preventing adhesion of aquatic organisms to, for example, ship bottoms, underwater structures, fish nets, and the like. Specifically, ships, fishing materials (eg ropes, fishing nets, floats, buoys), underwater structures such as thermal and nuclear power plants, drainage ports, gulf roads, submarine tunnels, harbor facilities, canals and waterways, etc. When applied to the surface of various base materials such as a sludge diffusion prevention film for various marine civil engineering works, the antifouling property is exhibited.
- the pigment can be blended in the range of 1 to 1000 parts by mass with respect to 100 parts by mass of these film-forming polymers.
- the antifouling paint can also contain xylene, ethanol, isopropanol and the like as an organic solvent.
- cuprous oxide-coated particles B1 The true specific gravity of the cuprous oxide-coated particle B1 was 3.1 g / cm 3 .
- Electrode Copper plate for both anode and cathode
- cuprous oxide-coated particles B4 The true specific gravity of the cuprous oxide-coated particles B4 was 1.2 g / cm 3 .
- Electrode Copper plate for both anode and cathode
- cuprous oxide-coated particles b2 were obtained in the same manner as in Example 2 except that the pH of the aqueous electrolyte solution was not adjusted. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition and exceeded 13. The true specific gravity of the obtained cuprous oxide-coated particles b2 was 1.1 g / cm 3 .
- cuprous oxide-coated particles obtained in Examples 2 to 5 are also formed from an aggregate of octahedral cuprous oxide particles, similar to the cuprous oxide-coated particles of Example 1. It was confirmed that this dense layer completely covered the surface of the core material. In these examples, 90 or more particles were octahedral with respect to 100 cuprous oxide particles to be observed.
- the cuprous oxide particles obtained in Comparative Examples 2 to 5 were amorphous.
- the mass ratio of the core material and cuprous oxide was 50/50 in Example 1, whereas it was 76/24 in Comparative Example 1, and in Comparative Example 1, It can be seen that the amount of cuprous oxide attached is small. As a result, the true specific gravity of the cuprous oxide-coated particles of Comparative Example 1 is considered to be lower than that of the cuprous oxide-coated particles of Example 1. The same measurement was performed on the cuprous oxide-coated particles of Examples 2 to 5 and Comparative Examples 2 to 5. The results are shown in Table 1 below.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
Disclosed are particles coated with cuprous oxide, each of which has high adhesion between a cuprous oxide layer and a core material. The particles coated with cuprous oxide are dispersed well in an antifouling coating material, and provides an antifouling coating material that has high storage stability. Specifically disclosed are particles coated with cuprous oxide, each of which is obtained by coating the surface of a core material with a cuprous oxide layer. The particles coated with cuprous oxide are characterized in that the cuprous oxide layer is configured of an assembly of octahedral cuprous oxide particles and completely covers the surface of the core material. The particles coated with cuprous oxide can be suitably produced by performing electrodeposition of cuprous oxide while maintaining the pH of the aqueous electrolyte solution at 7-13 during the electrodeposition process.
Description
本発明は、芯材の表面に亜酸化銅が被覆された亜酸化銅被覆粒子及びその製造方法に関する。本発明の亜酸化銅被覆粒子は、防汚塗料用の顔料として特に有用である。
The present invention relates to cuprous oxide-coated particles in which the surface of a core material is coated with cuprous oxide and a method for producing the same. The cuprous oxide-coated particles of the present invention are particularly useful as a pigment for antifouling paints.
亜酸化銅は、古くから防汚顔料として知られており、塗料化され、船底用塗料として、海中の貝類や藻類の付着を防止するために用いられている。亜酸化銅は、真比重が６．０と大きく、船底用塗料にした場合、ビヒクルと亜酸化銅との比重の差により、亜酸化銅が沈降してしまうという問題があった。また、近年の金属原料価格の高騰により、使用量を削減することが、業界の課題となっている。
Cuprous oxide has long been known as an antifouling pigment, has been made into a paint, and has been used as a ship bottom paint to prevent adhesion of shellfish and algae in the sea. Cuprous oxide has a large true specific gravity of 6.0, and when used as a ship bottom paint, there is a problem that the cuprous oxide settles due to the difference in specific gravity between the vehicle and the cuprous oxide. In addition, due to the recent rise in prices of metal raw materials, reducing the amount of use has become an issue for the industry.
比重を小さくする方法としては、芯材の表面に亜酸化銅を被覆することにより、比重を小さくする方法が考えられる。例えば、塩素イオンを含む水溶液中にＳｉＯ2及び又はＡｌ2Ｏ3を少なくとも含む粉を懸濁させた液を電解液とし、銅板を陽極として電解する防汚塗料用複合顔料の製造方法が提案されている（特許文献１参照）。
As a method of reducing the specific gravity, a method of reducing the specific gravity by coating the surface of the core material with cuprous oxide can be considered. For example, a method for producing a composite pigment for antifouling paints has been proposed in which a solution obtained by suspending a powder containing at least SiO 2 and / or Al 2 O 3 in an aqueous solution containing chlorine ions is used as an electrolyte and a copper plate is used as an anode for electrolysis. (See Patent Document 1).
しかしながら、特許文献１に記載の製造方法で得られた亜酸化銅被覆粉体には、亜酸化銅の密着性が悪いこと、防汚塗料中での分散性が悪いこと、防汚塗料の保存安定性が悪くなること等実用性に乏しいという問題があった。
However, the cuprous oxide-coated powder obtained by the production method described in Patent Document 1 has poor adhesion of cuprous oxide, poor dispersibility in the antifouling paint, and storage of the antifouling paint. There were problems such as poor stability and poor practicality.
本発明の目的は、前述した従来技術が有する種々の欠点を解消し得る亜酸化銅被覆粒子及びその製造方法並びに該亜酸化銅被覆粒子を含む防汚塗料を提供することにある。
An object of the present invention is to provide cuprous oxide-coated particles, a method for producing the same, and an antifouling paint containing the cuprous oxide-coated particles, which can eliminate the various disadvantages of the conventional techniques described above.
本発明は、芯材の表面が亜酸化銅の層で被覆されてなる亜酸化銅被覆粒子において、 前記亜酸化銅の層は、前記芯材の表面を完全被覆しているとともに、八面体状の亜酸化銅の粒子の集合体から構成されていることを特徴とする亜酸化銅被覆粒子を提供するものである。
The present invention relates to a cuprous oxide-coated particle in which the surface of a core material is coated with a cuprous oxide layer, wherein the cuprous oxide layer completely covers the surface of the core material and is octahedral. The present invention provides a cuprous oxide-coated particle comprising an aggregate of cuprous oxide particles.
また本発明は、前記の亜酸化銅被覆粒子の好適な製造方法として、
芯材を、第一スズ塩の水溶液、銀塩の水溶液及びパラジウム塩の水溶液のいずれか１種又は２種以上の表面処理水溶液に接触させて、芯材の表面処理物を得る表面処理工程と、
前記芯材の表面処理物を、電解質及び酸化防止剤を含有する電解液水溶液に分散させ、金属銅を陽極として用いて電解を行い、該芯材の表面処理物の表面に亜酸化銅を電着させて、亜酸化銅被覆粒子を得る電着工程とを有し、
電着工程における前記電解液水溶液のｐＨを７～１３に維持して亜酸化銅の電着を行うことを特徴とする亜酸化銅被覆粒子の製造方法を提供するものである。 In addition, the present invention provides a suitable method for producing the cuprous oxide-coated particles,
A surface treatment step of bringing the core material into contact with one or more surface treatment aqueous solutions of an aqueous solution of stannous salt, an aqueous solution of silver salt, and an aqueous solution of palladium salt to obtain a surface treatment product of the core material; ,
The surface treatment product of the core material is dispersed in an aqueous electrolyte solution containing an electrolyte and an antioxidant, electrolysis is performed using metallic copper as an anode, and cuprous oxide is charged on the surface of the surface treatment product of the core material. And having an electrodeposition step of obtaining cuprous oxide-coated particles,
The present invention provides a method for producing cuprous oxide-coated particles, characterized in that the electrodeposition of cuprous oxide is performed while maintaining the pH of the aqueous electrolyte solution in the electrodeposition step at 7 to 13.
芯材を、第一スズ塩の水溶液、銀塩の水溶液及びパラジウム塩の水溶液のいずれか１種又は２種以上の表面処理水溶液に接触させて、芯材の表面処理物を得る表面処理工程と、
前記芯材の表面処理物を、電解質及び酸化防止剤を含有する電解液水溶液に分散させ、金属銅を陽極として用いて電解を行い、該芯材の表面処理物の表面に亜酸化銅を電着させて、亜酸化銅被覆粒子を得る電着工程とを有し、
電着工程における前記電解液水溶液のｐＨを７～１３に維持して亜酸化銅の電着を行うことを特徴とする亜酸化銅被覆粒子の製造方法を提供するものである。 In addition, the present invention provides a suitable method for producing the cuprous oxide-coated particles,
A surface treatment step of bringing the core material into contact with one or more surface treatment aqueous solutions of an aqueous solution of stannous salt, an aqueous solution of silver salt, and an aqueous solution of palladium salt to obtain a surface treatment product of the core material; ,
The surface treatment product of the core material is dispersed in an aqueous electrolyte solution containing an electrolyte and an antioxidant, electrolysis is performed using metallic copper as an anode, and cuprous oxide is charged on the surface of the surface treatment product of the core material. And having an electrodeposition step of obtaining cuprous oxide-coated particles,
The present invention provides a method for producing cuprous oxide-coated particles, characterized in that the electrodeposition of cuprous oxide is performed while maintaining the pH of the aqueous electrolyte solution in the electrodeposition step at 7 to 13.
更に本発明は、前記の亜酸化銅被覆粒子を防汚塗料用の顔料として含む防汚塗料を提供するものである。
Furthermore, the present invention provides an antifouling paint comprising the cuprous oxide-coated particles as a pigment for the antifouling paint.
本発明によれば、芯材と亜酸化銅の層との密着性が高く、防汚塗料中での分散性が良く、かつ防汚塗料の保存安定性が高い亜酸化銅被覆粒子が提供される。
According to the present invention, cuprous oxide-coated particles having high adhesion between the core material and the cuprous oxide layer, good dispersibility in the antifouling paint, and high storage stability of the antifouling paint are provided. The
以下、本発明をその好ましい実施形態に基づき説明する。本発明の亜酸化銅被覆粒子は、芯材と、該芯材の表面を被覆する亜酸化銅（Ｃｕ2Ｏ）の層とで構成されている。本発明の亜酸化銅被覆粒子は、亜酸化銅の層が、芯材の表面を完全被覆している点に特徴の一つを有する。完全被覆とは、亜酸化銅被覆粒子を電子顕微鏡で観察した場合（例えば倍率２０００倍で観察した場合）に、芯材の表面の露出が観察されないように、亜酸化銅の層が該芯材の表面を覆っていることを言う。
Hereinafter, the present invention will be described based on preferred embodiments thereof. The cuprous oxide-coated particles of the present invention are composed of a core material and a cuprous oxide (Cu 2 O) layer that covers the surface of the core material. The cuprous oxide-coated particles of the present invention are characterized in that the cuprous oxide layer completely covers the surface of the core material. The complete coating means that when the cuprous oxide-coated particles are observed with an electron microscope (for example, when observed at a magnification of 2000 times), the layer of the cuprous oxide is not exposed to the surface of the core material. Say that it covers the surface.
本発明の亜酸化銅被覆粒子は、亜酸化銅の層が芯材の表面を完全被覆していることに加え、特定の構造を有している点も特徴の一つである。詳細には、亜酸化銅の層は、八面体状の亜酸化銅の粒子の集合体から構成されている。亜酸化銅の粒子は、複数個が緻密に集合して所定の厚みを有する層をなしている。亜酸化銅の層がこのような構造を有していることに起因して、本発明の亜酸化銅被覆粒子は、芯材と亜酸化銅の層との密着性が高くなると考えられる。また、防汚塗料中での分散性が良く、かつ防汚塗料の保存安定性が高くなると考えられる。なお、亜酸化銅の粒子が八面体状であることによって、これらの有利な効果が奏されることの技術的な理由については、更に検討すべき余地が残されている。
The cuprous oxide-coated particles of the present invention are also characterized by having a specific structure in addition to the cuprous oxide layer completely covering the surface of the core material. Specifically, the cuprous oxide layer is composed of an aggregate of octahedral cuprous oxide particles. A plurality of cuprous oxide particles are densely assembled to form a layer having a predetermined thickness. Due to the fact that the cuprous oxide layer has such a structure, the cuprous oxide-coated particles of the present invention are considered to have high adhesion between the core material and the cuprous oxide layer. Further, it is considered that the dispersibility in the antifouling paint is good and the storage stability of the antifouling paint is increased. In addition, the technical reason that these advantageous effects are achieved by the cuprous oxide particles being octahedral has room for further study.
亜酸化銅の層を構成する個々の亜酸化銅粒子は、そのすべてが八面体状であることが理想的であるが、すべての亜酸化銅粒子が八面体状であることは要しない。本発明者らが検討したところ、亜酸化銅の層を電子顕微鏡観察した場合に、観察対象となる亜酸化銅粒子１００個当たり好ましくは５０個以上、更に好ましくは６０個以上の亜酸化銅粒子が八面体状であれば、上述した有利な効果が奏される。
It is ideal that all of the individual cuprous oxide particles constituting the cuprous oxide layer have an octahedral shape, but it is not necessary that all the cuprous oxide particles have an octahedral shape. As a result of investigation by the present inventors, when the cuprous oxide layer is observed with an electron microscope, it is preferably 50 or more, more preferably 60 or more cuprous oxide particles per 100 cuprous oxide particles to be observed. If is octahedral, the above-described advantageous effects are exhibited.
八面体状の亜酸化銅粒子を含む層は、例えば後述する電解還元法によって亜酸化銅を生成させることで首尾よく形成することができる。これに対して無電解還元法で亜酸化銅を生成させると、後述する比較例１に示すように、立方体状の亜酸化銅粒子からなる層が形成されてしまう。このような構造の層を有する亜酸化銅被覆粒子は、芯材と亜酸化銅の層との密着性が十分に高くならず、またこれを防汚塗料用の顔料として用いた場合、防汚塗料中での分散性や保存安定性が劣るものとなってしまう。
The layer containing octahedral cuprous oxide particles can be successfully formed by, for example, producing cuprous oxide by the electrolytic reduction method described later. On the other hand, when cuprous oxide is produced by an electroless reduction method, a layer composed of cubic cuprous oxide particles is formed as shown in Comparative Example 1 described later. The cuprous oxide-coated particles having a layer having such a structure do not have sufficiently high adhesion between the core material and the cuprous oxide layer, and when this is used as a pigment for an antifouling paint, Dispersibility in the paint and storage stability will be poor.
八面体状の形状を有する亜酸化銅粒子は、その粒径が０.１～３μｍ、特に０．５～２μｍであることが好ましい。粒径がこの範囲内であることによって、該亜酸化銅粒子から構成される層が十分に緻密なものとなり、防汚塗料中での分散性や保存安定性が高くなる。亜酸化銅粒子の粒径は、走査型電子顕微鏡観察によって測定される。
The cuprous oxide particles having an octahedral shape preferably have a particle size of 0.1 to 3 μm, particularly 0.5 to 2 μm. When the particle size is within this range, the layer composed of the cuprous oxide particles becomes sufficiently dense, and the dispersibility and storage stability in the antifouling paint are increased. The particle size of the cuprous oxide particles is measured by observation with a scanning electron microscope.
亜酸化銅の層の厚みは、芯材の表面を完全被覆できる厚みであれば、その値に特に制限はない。亜酸化銅の層の厚みは、例えば該層の断面の走査型電子顕微鏡観察によって測定することができる。
The thickness of the cuprous oxide layer is not particularly limited as long as it can completely cover the surface of the core material. The thickness of the cuprous oxide layer can be measured, for example, by scanning electron microscope observation of the cross section of the layer.
八面体状の亜酸化銅の粒子は、これが規則正しく積み重なって層を形成してもよく、あるいはランダムに積み重なって層を形成してもよい。
The octahedral cuprous oxide particles may be stacked regularly to form a layer, or randomly stacked to form a layer.
亜酸化銅粒子の層の厚みに関連して、芯材と亜酸化銅との比率は、質量比で表して、好ましくは芯材／亜酸化銅＝９５／５～１０／９０という広範な範囲で設定可能であり、更に好ましく８０／２０～２０／８０である。この質量比は、目的とする亜酸化銅被覆粒子の比重が所望の範囲内となるように適切に設定すればよい。
In relation to the thickness of the cuprous oxide particle layer, the ratio of the core material to the cuprous oxide is preferably expressed as a mass ratio, preferably in a wide range of core material / cuprous oxide = 95/5 to 10/90. And more preferably 80/20 to 20/80. This mass ratio may be appropriately set so that the specific gravity of the target cuprous oxide-coated particles is within a desired range.
芯材としては、亜酸化銅被覆粒子の具体的な用途に応じ適切な材料のものが選択される。具体的には芯材として、珪酸含有無機化合物、アルカリ土類金属化合物、アルミナ、有機化合物等を用いることができる。珪酸含有無機化合物としては、例えば珪石、珪砂、石英などの結晶シリカ、結晶シリカを加熱溶融して所望により適宜成形した溶融シリカなどの非結晶シリカ、珪藻土、各種ゼオライト、タルク、クレイ、フライアッシュ、ガラスビーズ、ガラスバルーン、シラスバルーン等が挙げられる。アルカリ土類金属化合物としては、例えば硫酸バリウム、炭酸カルシウム等のアルカリ土類金属塩が挙げられる。有機化合物としては、例えば熱可塑性樹脂、熱硬化性樹脂等の高分子材料が挙げられる。具体的には、ポリエチレン、ポリプロピレン、アクリル樹脂、ポリスチレン、ポリエステル、フッ素樹脂、シリコン樹脂、フェノール樹脂、ユリア樹脂、メラミン樹脂、エポキシ樹脂等が挙げられる。
As the core material, an appropriate material is selected according to the specific use of the cuprous oxide-coated particles. Specifically, a silicic acid-containing inorganic compound, an alkaline earth metal compound, alumina, an organic compound, or the like can be used as the core material. Examples of silicic acid-containing inorganic compounds include, for example, crystalline silica such as silica, silica sand, and quartz, amorphous silica such as fused silica obtained by heating and melting crystalline silica as appropriate, diatomaceous earth, various zeolites, talc, clay, fly ash, Examples thereof include glass beads, glass balloons, and shirasu balloons. Examples of the alkaline earth metal compound include alkaline earth metal salts such as barium sulfate and calcium carbonate. Examples of the organic compound include polymer materials such as thermoplastic resins and thermosetting resins. Specific examples include polyethylene, polypropylene, acrylic resin, polystyrene, polyester, fluorine resin, silicon resin, phenol resin, urea resin, melamine resin, and epoxy resin.
芯材の粒径は、亜酸化銅被覆粒子の具体的な用途に応じて適切な値が選択される。亜酸化銅被覆粒子を例えば防汚塗料用の顔料として用いる場合には、体積基準粒度分布の平均粒子径Ｄ50で表して０．５～１００μｍ、特に２～５０μｍの芯材を用いることが、船底塗料特性の点から好ましい。特に、亜酸化銅の層の厚みが上述した範囲である場合に、この範囲の粒径の芯材を用いると、両者の密着性が一層良好になるので好ましい。Ｄ50は粒度分布測定装置によって測定される。
As the particle size of the core material, an appropriate value is selected according to the specific use of the cuprous oxide-coated particles. When using cuprous oxide-coated particles as a pigment for antifouling paints, for example, a core material of 0.5 to 100 μm, particularly 2 to 50 μm, expressed by an average particle size D 50 of a volume-based particle size distribution, This is preferable from the viewpoint of ship bottom paint characteristics. In particular, when the thickness of the cuprous oxide layer is in the above-described range, it is preferable to use a core material having a particle size in this range because the adhesiveness between the two becomes better. D 50 is measured by a particle size distribution measuring device.
粒径に関連して、芯材の形状も亜酸化銅被覆粒子の具体的な用途に応じて適切に選択できる。例えば球状、立方体状、板状、塊状等のものを用いることができる。一般には、球状の芯材を用いることで、満足すべき効果が得られる。また、芯材は、中実のものでもよく、あるいは中空のものでもよい。
In relation to the particle size, the shape of the core material can also be appropriately selected according to the specific use of the cuprous oxide-coated particles. For example, a spherical shape, a cubic shape, a plate shape, a lump shape, or the like can be used. In general, a satisfactory effect can be obtained by using a spherical core material. The core material may be solid or hollow.
次に、本発明の亜酸化銅被覆粒子の好適な製造方法について説明する。亜酸化銅被覆粒子は、芯材の表面に電解によって亜酸化銅粒子を生成させ、複数の該粒子を積み重ねて層となすことで得ることができる。本製造方法は、（イ）芯材の表面処理工程、（ロ）電解による亜酸化銅の電着工程、（ハ）亜酸化銅被覆粒子の水洗工程に大別される。以下、それぞれの工程について説明する。
Next, a preferred method for producing the cuprous oxide-coated particles of the present invention will be described. The cuprous oxide-coated particles can be obtained by producing cuprous oxide particles on the surface of the core material by electrolysis and stacking a plurality of the particles to form a layer. This production method is broadly divided into (a) a surface treatment process of the core material, (b) an electrodeposition process of cuprous oxide by electrolysis, and (c) a water washing process of cuprous oxide-coated particles. Hereinafter, each process will be described.
（イ）の芯材の表面処理工程においては、芯材を、第一スズ塩の水溶液、銀塩の水溶液及びパラジウム塩の水溶液のいずれか１種又は２種以上の表面処理水溶液に接触させて、芯材の表面処理物を得る。芯材が、熱可塑性樹脂、熱硬化性樹脂等の場合、具体的にはポリエチレン、ポリプロピレン、アクリル樹脂、ポリスチレン、ポリエステル、フッ素樹脂、シリコン樹脂、フェノール樹脂、ユリア樹脂、メラミン樹脂、エポキシ樹脂等の場合には、表面処理工程を行うに先立ち、アルカリ洗浄及び酸による表面粗化を行うことができる。つまり、表面処理工程を行う前に、芯材のアルカリ洗浄及び酸による表面粗化を行ってもよい。アルカリ洗浄するために用いられるアルカリとしては、例えば水酸化ナトリウム、炭酸ナトリウム、オルソケイ酸ナトリウム、ピロリン酸ナトリウム等が挙げられる。一方、酸によって表面粗化するために用いられる酸としては、例えば硫酸、硝酸、リン酸、クロム酸、塩酸、酢酸、フッ化水素酸等から選ばれる１種又はこれら２種以上の混酸等が挙げられる。
In the surface treatment step of the core material in (a), the core material is brought into contact with one or more surface treatment aqueous solutions of an aqueous solution of stannous salt, an aqueous solution of silver salt, and an aqueous solution of palladium salt. A surface treatment product of the core material is obtained. When the core material is a thermoplastic resin, a thermosetting resin, etc., specifically, polyethylene, polypropylene, acrylic resin, polystyrene, polyester, fluororesin, silicon resin, phenol resin, urea resin, melamine resin, epoxy resin, etc. In some cases, prior to the surface treatment step, surface cleaning with alkali and acid can be performed. That is, before performing the surface treatment step, the core material may be subjected to alkali cleaning and acid roughening. Examples of the alkali used for the alkali cleaning include sodium hydroxide, sodium carbonate, sodium orthosilicate, sodium pyrophosphate and the like. On the other hand, as the acid used for roughening the surface with an acid, for example, one kind selected from sulfuric acid, nitric acid, phosphoric acid, chromic acid, hydrochloric acid, acetic acid, hydrofluoric acid, etc., or a mixed acid of two or more of these may be used. Can be mentioned.
表面処理工程において用いられる表面処理水溶液は、上述のとおり第一スズ塩の水溶液、銀塩の水溶液及びパラジウム塩の水溶液のいずれか１種又は２種以上である。２種以上の水溶液を組み合わせて用いる場合には、銀塩とパラジウム塩との混合水溶液を用いることが好ましい。
As described above, the surface treatment aqueous solution used in the surface treatment step is one or more of a stannous salt aqueous solution, a silver salt aqueous solution, and a palladium salt aqueous solution. When two or more aqueous solutions are used in combination, a mixed aqueous solution of silver salt and palladium salt is preferably used.
表面処理水溶液に係る第一スズ塩の水溶液としては、例えばフッ化第一スズ水溶液、塩化第一スズ水溶液等のハロゲン化第一スズの水溶液、硫酸第一スズの水溶液等が挙げられる。また、表面処理水溶液に係る銀塩の水溶液としては、例えば硝酸銀、酢酸銀、硫酸銀の水溶液等が挙げられる。表面処理水溶液に係るパラジウム塩の水溶液としては、例えば塩化パラジウムの水溶液が挙げられる。
Examples of the stannous salt aqueous solution relating to the surface treatment aqueous solution include stannous halide aqueous solutions such as stannous fluoride aqueous solution and stannous chloride aqueous solution, and stannous sulfate aqueous solution. Examples of the aqueous silver salt solution used for the surface treatment aqueous solution include aqueous solutions of silver nitrate, silver acetate, and silver sulfate. Examples of the aqueous palladium salt solution for the surface treatment aqueous solution include an aqueous palladium chloride solution.
表面処理水溶液中の第一スズ塩、銀塩又はパラジウム塩の濃度は、それぞれ独立に好ましくは０.１～４０ｇ／Ｌ、特に好ましくは０．５～３０ｇ／Ｌである。
The concentration of stannous salt, silver salt or palladium salt in the surface treatment aqueous solution is preferably independently from 0.1 to 40 g / L, particularly preferably from 0.5 to 30 g / L.
表面処理工程において、芯材と表面処理水溶液とを接触させる方法としては、例えば表面処理水溶液中に芯材を加え、撹拌する方法が挙げられるが、これに制限されるものではない。
In the surface treatment step, examples of the method of bringing the core material into contact with the surface treatment aqueous solution include a method of adding the core material to the surface treatment aqueous solution and stirring, but the method is not limited thereto.
表面処理工程を行うときの表面処理水溶液の温度に特に制限はないが、０～７０℃、特に１０～５０℃に設定することが好ましい。
There is no particular limitation on the temperature of the surface treatment aqueous solution when performing the surface treatment step, but it is preferably set to 0 to 70 ° C, particularly 10 to 50 ° C.
表面処理工程では、芯材を表面処理水溶液に接触させた後、表面処理水溶液から芯材を分離し、芯材の表面処理物を得る。この場合、芯材を、一種類の表面処理水溶液とのみ接触させてもよく、あるいは芯材を一の表面処理水溶液と接触させた後に分離し、更に他の表面処理水溶液に接触させ、分離するというように、２種類以上の表面処理水溶液と順次接触させてもよい。
In the surface treatment step, after the core material is brought into contact with the surface treatment aqueous solution, the core material is separated from the surface treatment aqueous solution to obtain a surface treated product of the core material. In this case, the core material may be brought into contact with only one type of surface treatment aqueous solution, or separated after the core material is brought into contact with one surface treatment aqueous solution, and further contacted with another surface treatment aqueous solution and separated. As such, it may be sequentially brought into contact with two or more kinds of surface treatment aqueous solutions.
表面処理を行った後、表面処理水溶液と芯材とを分離する方法としては、ブフナー濾過、遠心分離等が挙げられる。表面処理水溶液から分離した芯材の表面処理物は、必要に応じて乾燥してもよい。
Examples of methods for separating the surface treatment aqueous solution and the core material after the surface treatment include Buchner filtration and centrifugation. The surface treatment product of the core material separated from the surface treatment aqueous solution may be dried as necessary.
このようにして得られた芯材の表面処理物は、次いで（ロ）の電解による亜酸化銅の電着工程に付される。本工程においては、芯材の表面処理物を電解液水溶液に分散させ、金属銅を陽極として、該表面処理物の表面に亜酸化銅を電着させて、亜酸化銅被覆粒子を得る。
The surface treatment of the core material obtained in this way is then subjected to a cuprous oxide electrodeposition step by electrolysis (b). In this step, the surface treatment product of the core material is dispersed in an aqueous electrolyte solution, and cuprous oxide is electrodeposited on the surface of the surface treatment product using metal copper as an anode to obtain cuprous oxide-coated particles.
前記の電解液水溶液は、電解質及び酸化防止剤を含有する。電解質としては、例えば塩化ナトリウムや塩化カリウム等の塩化物を用いることができる。一方、酸化防止剤としては、例えばグリセリン、クエン酸、糖類等を用いることができる。
The aqueous electrolyte solution contains an electrolyte and an antioxidant. As the electrolyte, for example, chlorides such as sodium chloride and potassium chloride can be used. On the other hand, as the antioxidant, for example, glycerin, citric acid, saccharides and the like can be used.
電解液水溶液中の塩化物の濃度は、塩素イオンの濃度で表して好ましくは２０～２００ｇ／Ｌ、更に好ましくは２０～１５０ｇ／Ｌである。一方、酸化防止剤の濃度は、好ましくは０．３～６０ｇ／Ｌ、更に好ましくは０．５～４０ｇ／Ｌである。
The chloride concentration in the aqueous electrolyte solution is preferably 20 to 200 g / L, more preferably 20 to 150 g / L, expressed as the concentration of chlorine ions. On the other hand, the concentration of the antioxidant is preferably 0.3 to 60 g / L, more preferably 0.5 to 40 g / L.
電解液水溶液に分散させる芯材の表面処理物の量は、電解液水溶液に対して、好ましくは１～８０ｇ／Ｌ、更に好ましくは１～６０ｇ／Ｌである。この範囲内に設定することで、電着時における芯材どうしの凝集を抑制しつつ、電着の効率を高めることができる。
The amount of the surface treatment product of the core material dispersed in the aqueous electrolyte solution is preferably 1 to 80 g / L, more preferably 1 to 60 g / L with respect to the aqueous electrolyte solution. By setting within this range, the efficiency of electrodeposition can be enhanced while suppressing aggregation of the core materials during electrodeposition.
電着工程においては上述のとおり陽極として金属銅を用いる。この金属銅としては通常金属銅板を用いればよい。金属銅の純度は９９％以上であればよい。一方、陰極としては、板状の金属銅やステンレスを用いることができる。
In the electrodeposition process, metallic copper is used as the anode as described above. As this metallic copper, a metallic copper plate may be usually used. The purity of metallic copper should just be 99% or more. On the other hand, plate-like metallic copper or stainless steel can be used as the cathode.
電着工程では、芯材の表面処理物を、電解液水溶液に加え、電解液水溶液を撹拌して、芯材の表面処理を分散させた状態下に通電を行うことで、芯材の表面処理物の表面に亜酸化銅を電着させる。
In the electrodeposition process, the surface treatment of the core material is performed by adding the surface treatment product of the core material to the aqueous electrolyte solution and stirring the aqueous electrolyte solution to disperse the surface treatment of the core material. Electrodeposit cuprous oxide on the surface of the object.
電着温度は１０～７０℃が好ましい。温度をこの範囲内に設定することで、電着に伴うガスの発生及びそれに起因する亜酸化銅と芯材表面との密着性の低下を抑制しつつ、電着速度を高めることが可能となる。また、電着の際の電流密度は、好ましくは１～３０Ａ／ｄｍ2、更に好ましくは１～１０Ａ／ｄｍ2である。電流密度をこの範囲内に設定することで、ガスの発生等を抑制しつつ、効率よく電着を行うことができる。
The electrodeposition temperature is preferably 10 to 70 ° C. By setting the temperature within this range, it is possible to increase the electrodeposition speed while suppressing the generation of gas accompanying electrodeposition and the decrease in the adhesion between the cuprous oxide and the core material surface resulting therefrom. . The current density during electrodeposition is preferably 1 to 30 A / dm 2 , more preferably 1 to 10 A / dm 2 . By setting the current density within this range, it is possible to efficiently perform electrodeposition while suppressing the generation of gas and the like.
電着工程においては、電着の間の電解液水溶液のｐＨを監視しながら、該ｐＨを７～１３、好ましくは８～１２、更に好ましくは９～１１に維持して亜酸化銅の電着を行うことが重要である。これによって、八面体状の形状を有する亜酸化銅粒子を首尾良く生成させることができる。電着を行うと電解液水溶液のｐＨが徐々に上昇するところ、例えば酸を加えてｐＨを低下させて、電解液水溶液のｐＨを上述の範囲内に維持する。ｐＨの調整に用いられる酸としては、例えば塩酸、硫酸、硝酸、臭素酸等が挙げられる。なお、電着を開始する前の電解液水溶液のｐＨは２～１２、特に４～１０に設定することが好ましい。
In the electrodeposition step, while monitoring the pH of the aqueous electrolyte solution during electrodeposition, the pH is maintained at 7 to 13, preferably 8 to 12, and more preferably 9 to 11, and cuprous oxide is electrodeposited. It is important to do. Thereby, cuprous oxide particles having an octahedral shape can be successfully generated. When the electrodeposition is performed, the pH of the aqueous electrolyte solution gradually increases. For example, an acid is added to lower the pH to maintain the pH of the aqueous electrolyte solution within the above range. Examples of the acid used for adjusting the pH include hydrochloric acid, sulfuric acid, nitric acid, bromic acid and the like. The pH of the aqueous electrolytic solution before starting electrodeposition is preferably set to 2 to 12, particularly 4 to 10.
芯材の表面に形成される亜酸化銅の層の厚み、つまり亜酸化銅の被覆量は、電着時間によって調節することができる。目的とする亜酸化銅被覆粒子の具体的な用途にもよるが、該粒子を防汚塗料用の顔料として用いる場合には、通常、１０分～４時間程度の電着時間を採用することが好適である。
The thickness of the cuprous oxide layer formed on the surface of the core material, that is, the coating amount of the cuprous oxide can be adjusted by the electrodeposition time. Depending on the specific use of the target cuprous oxide-coated particle, when the particle is used as a pigment for an antifouling paint, it is usually possible to employ an electrodeposition time of about 10 minutes to 4 hours. Is preferred.
このようにして電着が完了したら、ブフナー濾過や遠心分離等の手段を用いて電解液水溶液から亜酸化銅被覆粒子を分離する。次に、この粒子を（ハ）の水洗工程に付す。亜酸化銅被覆粒子を水洗する方法としては、リパルプ洗浄が一般的である。リパルプ洗浄を行う場合には、亜酸化銅被覆粒子と水との混合スラリーにおける亜酸化銅被覆粒子の濃度を、好ましくは５～２０質量％とする。洗浄時間は１０～６０分とすれば十分である。洗浄水としては、１０～７０℃の温水を使用することができる。
When electrodeposition is thus completed, cuprous oxide-coated particles are separated from the aqueous electrolyte solution using means such as Buchner filtration or centrifugation. Next, this particle | grain is attached | subjected to the water washing process of (c). Repulp washing is a common method for washing the cuprous oxide-coated particles with water. When performing repulp washing, the concentration of the cuprous oxide-coated particles in the mixed slurry of the cuprous oxide-coated particles and water is preferably 5 to 20% by mass. A washing time of 10 to 60 minutes is sufficient. As washing water, hot water of 10 to 70 ° C. can be used.
水洗工程では、亜酸化銅被覆粒子を、酸化防止剤を含有する洗浄水で洗浄することが、亜酸化銅が酸化することを防ぐ点から好ましい。酸化防止剤としては、例えばグリセリンや糖類等を用いることができる。洗浄水中の酸化防止剤の濃度は、好ましくは０．３～６０ｇ／Ｌ、特に好ましくは０．５～４０ｇ／Ｌである。
In the water washing step, it is preferable to wash the cuprous oxide-coated particles with washing water containing an antioxidant from the viewpoint of preventing the cuprous oxide from being oxidized. As antioxidant, glycerol, saccharides, etc. can be used, for example. The concentration of the antioxidant in the washing water is preferably 0.3 to 60 g / L, particularly preferably 0.5 to 40 g / L.
水洗が完了したら、洗浄液から亜酸化銅被覆粒子を分離し、乾燥する。このようにして目的とする亜酸化銅被覆粒子を得る。
After completion of washing with water, the cuprous oxide-coated particles are separated from the washing solution and dried. In this way, target cuprous oxide-coated particles are obtained.
上述の方法で亜酸化銅被覆粒子を製造すると、亜酸化銅の付き回り及び密着性が良くなるので、亜酸化銅の層の密着性が高くなり、かつ亜酸化銅の単独生成粒子や亜酸化銅被覆粒子の凝集体を、極めて少なくすることができる。
When the cuprous oxide-coated particles are produced by the above-described method, the adhesion and adhesion of the cuprous oxide are improved, so that the adhesion of the cuprous oxide layer is increased, and the cuprous oxide single-generated particles and the sub-oxide are produced. Aggregates of copper-coated particles can be extremely reduced.
このようにして得られた亜酸化銅被覆粒子は、例えば防汚塗料用の顔料として特に好適に用いられる。この防汚塗料は、例えば船底、水中構造物、魚網などへの水棲生物の付着防止に用いられる。具体的には、船舶、漁業資材（例：ロープ、漁網、浮き子、ブイ）、火力・原子力発電所の給排水口等の水中構造物、湾岸道路、海底トンネル、港湾設備、運河・水路等のような各種海洋土木工事の汚泥拡散防止膜などの各種基材の表面に、１回ないし複数回塗布すれば防汚性が発揮される。
The cuprous oxide-coated particles thus obtained are particularly suitably used as a pigment for antifouling paints, for example. This antifouling paint is used for preventing adhesion of aquatic organisms to, for example, ship bottoms, underwater structures, fish nets, and the like. Specifically, ships, fishing materials (eg ropes, fishing nets, floats, buoys), underwater structures such as thermal and nuclear power plants, drainage ports, gulf roads, submarine tunnels, harbor facilities, canals and waterways, etc. When applied to the surface of various base materials such as a sludge diffusion prevention film for various marine civil engineering works, the antifouling property is exhibited.
防汚塗料は、一般に被膜形成性重合体と顔料とを含有するものであり、該顔料として本発明の亜酸化銅被覆粒子が用いられる。被膜形成性重合体としては、当該技術分野において従来用いられてきたものと同様のものを用いることができる。例えば（メタ）アクリル酸トリメチルシリルエステル、（メタ）アクリル酸トリエチルシリルエステル、（メタ）アクリル酸トリプロピルシリルエステル、（メタ）アクリル酸トリブチルシリルエステル、（メタ）アクリル酸ジメチルプロピルシリルエステル、（メタ）アクリル酸モノメチルジプロピルシリルエステル、（メタ）アクリル酸メチルエチルプロピルシリルエステル等の重合性不飽和カルボン酸のトリアルキルシリルエステルから誘導される成分単位を含む重合体；（メタ）アクリル酸ヒドロキシ金属塩成分単位等の重合性不飽和カルボン酸金属化合物成分単位を含有する重合体；γ－メタクリロイルオキシプロピルポリジメチルシロキサン等の分子中に重合性不飽和基とシロキサン結合部位を有する重合性不飽和モノマー及び該モノマーと共重合可能なその他の重合性不飽和モノマーを共重合成分として含有するビニル系共重合体；ウレタン樹脂などが挙げられる。顔料は、これらの被膜形成性重合体１００質量部に対して１～１０００質量部の範囲で配合することができる。また、防汚塗料は、これらの成分に加え、有機溶媒としてのキシレンやエタノール、イソプロパノールなどを含有することもできる。
The antifouling paint generally contains a film-forming polymer and a pigment, and the cuprous oxide-coated particles of the present invention are used as the pigment. As the film-forming polymer, those similar to those conventionally used in the technical field can be used. For example, (meth) acrylic acid trimethylsilyl ester, (meth) acrylic acid triethylsilyl ester, (meth) acrylic acid tripropylsilyl ester, (meth) acrylic acid tributylsilyl ester, (meth) acrylic acid dimethylpropylsilyl ester, (meth) Polymer containing component units derived from trialkylsilyl ester of polymerizable unsaturated carboxylic acid such as monomethyldipropylsilyl acrylate, methylethylpropyl silyl acrylate, etc .; (meth) acrylic acid hydroxy metal salt Polymers containing polymerizable unsaturated carboxylic acid metal compound component units such as component units; polymerizable unsaturated monomers having a polymerizable unsaturated group and a siloxane bonding site in the molecule, such as γ-methacryloyloxypropyl polydimethylsiloxane; Vinyl copolymer containing a monomer copolymerizable with the polymerizable unsaturated monomer as a copolymer component; and urethane resins. The pigment can be blended in the range of 1 to 1000 parts by mass with respect to 100 parts by mass of these film-forming polymers. In addition to these components, the antifouling paint can also contain xylene, ethanol, isopropanol and the like as an organic solvent.
以下、実施例により本発明を更に詳細に説明する。しかしながら本発明の範囲は、かかる実施例に制限されない。特に断らない限り、「％」は「質量％」を意味する。
Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to such examples. Unless otherwise specified, “%” means “mass%”.
〔実施例１〕
（１）表面処理工程
芯材としてのシリカ粉（平均粒子径Ｄ５０＝２０μｍ）を、フッ化スズ水溶液（１ｇ／Ｌ）に分散させ、撹拌し、濾過後、水洗し、更に硝酸銀水溶液（１ｇ／Ｌ）に分散させ、撹拌し、濾過後、水洗し、乾燥して、芯材の表面処理物Ａ１を得た。 [Example 1]
(1) Surface treatment step Silica powder (average particle diameter D 50 = 20 μm) as a core material is dispersed in an aqueous tin fluoride solution (1 g / L), stirred, filtered, washed with water, and further an aqueous silver nitrate solution (1 g). / L), stirred, filtered, washed with water, and dried to obtain a core surface-treated product A1.
（１）表面処理工程
芯材としてのシリカ粉（平均粒子径Ｄ５０＝２０μｍ）を、フッ化スズ水溶液（１ｇ／Ｌ）に分散させ、撹拌し、濾過後、水洗し、更に硝酸銀水溶液（１ｇ／Ｌ）に分散させ、撹拌し、濾過後、水洗し、乾燥して、芯材の表面処理物Ａ１を得た。 [Example 1]
(1) Surface treatment step Silica powder (average particle diameter D 50 = 20 μm) as a core material is dispersed in an aqueous tin fluoride solution (1 g / L), stirred, filtered, washed with water, and further an aqueous silver nitrate solution (1 g). / L), stirred, filtered, washed with water, and dried to obtain a core surface-treated product A1.
（２）電着工程及び水洗工程
次いで、芯材の表面処理物Ａ１ １０ｇを、電解液水溶液１Ｌに加え、電極を設置し、マグネチックスターラーで撹拌しながら、以下の条件で、３６分間通電し、芯材の表面処理物Ａ１に亜酸化銅を電着させた。電着の進行につれて電解液水溶液のｐＨが上昇したが、塩酸（濃度：２％）を適宜添加して該水溶液のｐＨを９～１０の範囲に維持した。次いで、電解液水溶液を濾過し、濾過物を水洗後、グリセリン水溶液に分散後濾過、乾燥し、亜酸化銅被覆粒子Ｂ１ ２１ｇを得た。亜酸化銅被覆粒子Ｂ１の真比重は３．１ｇ／ｃｍ3であった。 (2) Electrodeposition step and water washing step Next, 10 g of the surface treatment product A1 of the core material was added to 1 L of the aqueous electrolyte solution, an electrode was installed, and the mixture was stirred for 36 minutes under the following conditions while stirring with a magnetic stirrer. Then, cuprous oxide was electrodeposited on the surface treatment product A1 of the core material. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition, but hydrochloric acid (concentration: 2%) was appropriately added to maintain the pH of the aqueous solution in the range of 9-10. Next, the aqueous electrolyte solution was filtered, the filtrate was washed with water, dispersed in a glycerin aqueous solution, filtered and dried to obtain 21 g of cuprous oxide-coated particles B1. The true specific gravity of the cuprous oxide-coated particle B1 was 3.1 g / cm 3 .
次いで、芯材の表面処理物Ａ１ １０ｇを、電解液水溶液１Ｌに加え、電極を設置し、マグネチックスターラーで撹拌しながら、以下の条件で、３６分間通電し、芯材の表面処理物Ａ１に亜酸化銅を電着させた。電着の進行につれて電解液水溶液のｐＨが上昇したが、塩酸（濃度：２％）を適宜添加して該水溶液のｐＨを９～１０の範囲に維持した。次いで、電解液水溶液を濾過し、濾過物を水洗後、グリセリン水溶液に分散後濾過、乾燥し、亜酸化銅被覆粒子Ｂ１ ２１ｇを得た。亜酸化銅被覆粒子Ｂ１の真比重は３．１ｇ／ｃｍ3であった。 (2) Electrodeposition step and water washing step Next, 10 g of the surface treatment product A1 of the core material was added to 1 L of the aqueous electrolyte solution, an electrode was installed, and the mixture was stirred for 36 minutes under the following conditions while stirring with a magnetic stirrer. Then, cuprous oxide was electrodeposited on the surface treatment product A1 of the core material. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition, but hydrochloric acid (concentration: 2%) was appropriately added to maintain the pH of the aqueous solution in the range of 9-10. Next, the aqueous electrolyte solution was filtered, the filtrate was washed with water, dispersed in a glycerin aqueous solution, filtered and dried to obtain 21 g of cuprous oxide-coated particles B1. The true specific gravity of the cuprous oxide-coated particle B1 was 3.1 g / cm 3 .
＜電解液水溶液＞
塩化ナトリウム：２５０ｇ／Ｌ（塩素イオン濃度１５２ｇ／Ｌ）
グリセリン ：１０ｇ／Ｌ
ｐＨ ：７
＜処理条件＞
電流密度 ：７Ａ／ｄｍ2
電解液水溶液の液温 ：４０℃
電極 ：陽極及び陰極のいずれも銅板 <Electrolytic solution aqueous solution>
Sodium chloride: 250 g / L (chlorine ion concentration 152 g / L)
Glycerin: 10 g / L
pH: 7
<Processing conditions>
Current density: 7 A / dm 2
Liquid temperature of the aqueous electrolyte solution: 40 ° C
Electrode: Copper plate for both anode and cathode
塩化ナトリウム：２５０ｇ／Ｌ（塩素イオン濃度１５２ｇ／Ｌ）
グリセリン ：１０ｇ／Ｌ
ｐＨ ：７
＜処理条件＞
電流密度 ：７Ａ／ｄｍ2
電解液水溶液の液温 ：４０℃
電極 ：陽極及び陰極のいずれも銅板 <Electrolytic solution aqueous solution>
Sodium chloride: 250 g / L (chlorine ion concentration 152 g / L)
Glycerin: 10 g / L
pH: 7
<Processing conditions>
Current density: 7 A / dm 2
Liquid temperature of the aqueous electrolyte solution: 40 ° C
Electrode: Copper plate for both anode and cathode
〔実施例２〕
（１）表面処理工程
芯材としてのフライアッシュ（平均粒子径Ｄ５０＝４１μｍ）を、硝酸銀水溶液（１ｇ／Ｌ）に分散させ、撹拌し、濾過後、水洗し、乾燥して、芯材の表面処理物Ａ２を得た。 [Example 2]
(1) Surface treatment step Fly ash (average particle diameter D 50 = 41 μm) as a core material is dispersed in an aqueous silver nitrate solution (1 g / L), stirred, filtered, washed with water, and dried. Surface-treated product A2 was obtained.
（１）表面処理工程
芯材としてのフライアッシュ（平均粒子径Ｄ５０＝４１μｍ）を、硝酸銀水溶液（１ｇ／Ｌ）に分散させ、撹拌し、濾過後、水洗し、乾燥して、芯材の表面処理物Ａ２を得た。 [Example 2]
(1) Surface treatment step Fly ash (average particle diameter D 50 = 41 μm) as a core material is dispersed in an aqueous silver nitrate solution (1 g / L), stirred, filtered, washed with water, and dried. Surface-treated product A2 was obtained.
（２）電着工程及び水洗工程
次いで、芯材の表面処理物Ａ２ １０ｇを、電解液水溶液１Ｌに加え、電極を設置し、マグネチックスターラーで撹拌しながら、以下の条件で、１８分間通電し、芯材の表面処理物Ａ２に亜酸化銅を電着させた。電着の進行につれて電解液水溶液のｐＨが上昇したが、塩酸（濃度：２％）を適宜添加して該水溶液のｐＨを９～１０の範囲に維持した。次いで、電解液水溶液を濾過し、濾過物を水洗後、グリセリン水溶液に分散後濾過、乾燥し、亜酸化銅被覆粒子Ｂ２ １６ｇを得た。亜酸化銅被覆粒子Ｂ２の真比重は１．２ｇ／ｃｍ3であった。 (2) Electrodeposition process and water washing process Next, 10 g of the surface treatment product A2 of the core material was added to 1 L of the electrolyte aqueous solution, an electrode was installed, and the mixture was stirred for 18 minutes under the following conditions while stirring with a magnetic stirrer. Then, cuprous oxide was electrodeposited on the surface treated product A2 of the core material. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition, but hydrochloric acid (concentration: 2%) was appropriately added to maintain the pH of the aqueous solution in the range of 9-10. Next, the aqueous electrolyte solution was filtered, the filtrate was washed with water, dispersed in a glycerin aqueous solution, filtered and dried to obtain 16 g of cuprous oxide-coated particles B2. The true specific gravity of the cuprous oxide-coated particle B2 was 1.2 g / cm 3 .
次いで、芯材の表面処理物Ａ２ １０ｇを、電解液水溶液１Ｌに加え、電極を設置し、マグネチックスターラーで撹拌しながら、以下の条件で、１８分間通電し、芯材の表面処理物Ａ２に亜酸化銅を電着させた。電着の進行につれて電解液水溶液のｐＨが上昇したが、塩酸（濃度：２％）を適宜添加して該水溶液のｐＨを９～１０の範囲に維持した。次いで、電解液水溶液を濾過し、濾過物を水洗後、グリセリン水溶液に分散後濾過、乾燥し、亜酸化銅被覆粒子Ｂ２ １６ｇを得た。亜酸化銅被覆粒子Ｂ２の真比重は１．２ｇ／ｃｍ3であった。 (2) Electrodeposition process and water washing process Next, 10 g of the surface treatment product A2 of the core material was added to 1 L of the electrolyte aqueous solution, an electrode was installed, and the mixture was stirred for 18 minutes under the following conditions while stirring with a magnetic stirrer. Then, cuprous oxide was electrodeposited on the surface treated product A2 of the core material. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition, but hydrochloric acid (concentration: 2%) was appropriately added to maintain the pH of the aqueous solution in the range of 9-10. Next, the aqueous electrolyte solution was filtered, the filtrate was washed with water, dispersed in a glycerin aqueous solution, filtered and dried to obtain 16 g of cuprous oxide-coated particles B2. The true specific gravity of the cuprous oxide-coated particle B2 was 1.2 g / cm 3 .
＜電解液水溶液＞
塩化ナトリウム：２００ｇ／Ｌ（塩素イオン濃度１２１ｇ／Ｌ）
グリセリン ：１０ｇ／Ｌ
ｐＨ ：７
＜処理条件＞
電流密度 ：７Ａ／ｄｍ2
電解液水溶液の液温 ：３０℃
電極 ：陽極及び陰極のいずれも銅板 <Electrolytic solution aqueous solution>
Sodium chloride: 200 g / L (chlorine ion concentration 121 g / L)
Glycerin: 10 g / L
pH: 7
<Processing conditions>
Current density: 7 A / dm 2
Liquid temperature of electrolyte aqueous solution: 30 ° C
Electrode: Copper plate for both anode and cathode
塩化ナトリウム：２００ｇ／Ｌ（塩素イオン濃度１２１ｇ／Ｌ）
グリセリン ：１０ｇ／Ｌ
ｐＨ ：７
＜処理条件＞
電流密度 ：７Ａ／ｄｍ2
電解液水溶液の液温 ：３０℃
電極 ：陽極及び陰極のいずれも銅板 <Electrolytic solution aqueous solution>
Sodium chloride: 200 g / L (chlorine ion concentration 121 g / L)
Glycerin: 10 g / L
pH: 7
<Processing conditions>
Current density: 7 A / dm 2
Liquid temperature of electrolyte aqueous solution: 30 ° C
Electrode: Copper plate for both anode and cathode
〔実施例３〕
（１）表面処理工程
芯材としての珪石粉（平均粒子径Ｄ５０＝３２μｍ）を、フッ化スズ水溶液（１ｇ／Ｌ）に分散させ、撹拌し、濾過後、水洗し、更に塩酸含有塩化パラジウム水溶液（塩化パラジウム：０．２ｇ／Ｌ、塩酸１ｍｌ／Ｌ）に分散させ、撹拌し、濾過後、水洗し、乾燥して、芯材の表面処理物Ａ３を得た。 Example 3
(1) Surface treatment step Silica powder (average particle size D 50 = 32 μm) as a core material is dispersed in an aqueous tin fluoride solution (1 g / L), stirred, filtered, washed with water, and further hydrochloric acid-containing palladium chloride. It was dispersed in an aqueous solution (palladium chloride: 0.2 g / L, hydrochloric acid 1 ml / L), stirred, filtered, washed with water, and dried to obtain a core surface-treated product A3.
（１）表面処理工程
芯材としての珪石粉（平均粒子径Ｄ５０＝３２μｍ）を、フッ化スズ水溶液（１ｇ／Ｌ）に分散させ、撹拌し、濾過後、水洗し、更に塩酸含有塩化パラジウム水溶液（塩化パラジウム：０．２ｇ／Ｌ、塩酸１ｍｌ／Ｌ）に分散させ、撹拌し、濾過後、水洗し、乾燥して、芯材の表面処理物Ａ３を得た。 Example 3
(1) Surface treatment step Silica powder (average particle size D 50 = 32 μm) as a core material is dispersed in an aqueous tin fluoride solution (1 g / L), stirred, filtered, washed with water, and further hydrochloric acid-containing palladium chloride. It was dispersed in an aqueous solution (palladium chloride: 0.2 g / L, hydrochloric acid 1 ml / L), stirred, filtered, washed with water, and dried to obtain a core surface-treated product A3.
（２）電着工程及び水洗工程
次いで、芯材の表面処理物Ａ３ １０ｇを、電解液水溶液１Ｌに加え、電極を設置し、マグネチックスターラーで撹拌しながら、以下の条件で、２５分間通電し、芯材の表面処理物Ａ３に亜酸化銅を電着させた。電着の進行につれて電解液水溶液のｐＨが上昇したが、塩酸（濃度：２％）を適宜添加して該水溶液のｐＨを９～１０の範囲に維持した。次いで、電解液水溶液を濾過し、濾過物を水洗後、グリセリン水溶液に分散後濾過、乾燥し、亜酸化銅被覆粒子Ｂ３ １６ｇを得た。亜酸化銅被覆粒子Ｂ３の真比重は３．２ｇ／ｃｍ3であった。
＜電解液水溶液＞
塩化ナトリウム：２００ｇ／Ｌ（塩素イオン濃度１２１ｇ／Ｌ）
グリセリン ：１０ｇ／Ｌ
ｐＨ ：７
＜処理条件＞
電流密度 ：５Ａ／ｄｍ2
電解液水溶液の液温 ：５０℃
電極 ：陽極及び陰極のいずれも銅板 (2) Electrodeposition process and water washing process Next, 10 g of the surface treatment product A3 of the core material was added to 1 L of the aqueous electrolyte solution, an electrode was installed, and the mixture was energized for 25 minutes under the following conditions while stirring with a magnetic stirrer. Then, cuprous oxide was electrodeposited on the surface treatment product A3 of the core material. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition, but hydrochloric acid (concentration: 2%) was appropriately added to maintain the pH of the aqueous solution in the range of 9-10. Next, the aqueous electrolyte solution was filtered, and the filtrate was washed with water, dispersed in a glycerin aqueous solution, filtered and dried to obtain 16 g of cuprous oxide-coated particles B3. The true specific gravity of the cuprous oxide-coated particle B3 was 3.2 g / cm 3 .
<Electrolytic solution aqueous solution>
Sodium chloride: 200 g / L (chlorine ion concentration 121 g / L)
Glycerin: 10 g / L
pH: 7
<Processing conditions>
Current density: 5 A / dm 2
Solution temperature of electrolyte solution: 50 ° C
Electrode: Copper plate for both anode and cathode
次いで、芯材の表面処理物Ａ３ １０ｇを、電解液水溶液１Ｌに加え、電極を設置し、マグネチックスターラーで撹拌しながら、以下の条件で、２５分間通電し、芯材の表面処理物Ａ３に亜酸化銅を電着させた。電着の進行につれて電解液水溶液のｐＨが上昇したが、塩酸（濃度：２％）を適宜添加して該水溶液のｐＨを９～１０の範囲に維持した。次いで、電解液水溶液を濾過し、濾過物を水洗後、グリセリン水溶液に分散後濾過、乾燥し、亜酸化銅被覆粒子Ｂ３ １６ｇを得た。亜酸化銅被覆粒子Ｂ３の真比重は３．２ｇ／ｃｍ3であった。
＜電解液水溶液＞
塩化ナトリウム：２００ｇ／Ｌ（塩素イオン濃度１２１ｇ／Ｌ）
グリセリン ：１０ｇ／Ｌ
ｐＨ ：７
＜処理条件＞
電流密度 ：５Ａ／ｄｍ2
電解液水溶液の液温 ：５０℃
電極 ：陽極及び陰極のいずれも銅板 (2) Electrodeposition process and water washing process Next, 10 g of the surface treatment product A3 of the core material was added to 1 L of the aqueous electrolyte solution, an electrode was installed, and the mixture was energized for 25 minutes under the following conditions while stirring with a magnetic stirrer. Then, cuprous oxide was electrodeposited on the surface treatment product A3 of the core material. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition, but hydrochloric acid (concentration: 2%) was appropriately added to maintain the pH of the aqueous solution in the range of 9-10. Next, the aqueous electrolyte solution was filtered, and the filtrate was washed with water, dispersed in a glycerin aqueous solution, filtered and dried to obtain 16 g of cuprous oxide-coated particles B3. The true specific gravity of the cuprous oxide-coated particle B3 was 3.2 g / cm 3 .
<Electrolytic solution aqueous solution>
Sodium chloride: 200 g / L (chlorine ion concentration 121 g / L)
Glycerin: 10 g / L
pH: 7
<Processing conditions>
Current density: 5 A / dm 2
Solution temperature of electrolyte solution: 50 ° C
Electrode: Copper plate for both anode and cathode
〔実施例４〕
（１）表面処理工程
芯材としてのポリエチレン粉（平均粒子径Ｄ５０＝２０μｍ）を、水酸化ナトリウム水溶液で洗浄し、次いで、クロム酸、硫酸及びリン酸の混酸により表面粗化した後、フッ化スズ水溶液（１ｇ／Ｌ）に分散させ、撹拌し、濾過後、水洗し、更に硝酸銀水溶液（１ｇ／Ｌ）に分散させ、撹拌し、濾過後、水洗し、乾燥して、芯材の表面処理物Ａ４を得た。 Example 4
(1) Surface treatment step After the polyethylene powder (average particle diameter D 50 = 20 μm) as a core material is washed with an aqueous sodium hydroxide solution and then surface-roughened with a mixed acid of chromic acid, sulfuric acid and phosphoric acid, fluorine Disperse in tin chloride aqueous solution (1 g / L), stir, filter, wash with water, further disperse in silver nitrate aqueous solution (1 g / L), stir, filter, wash with water, dry, surface of core A processed product A4 was obtained.
（１）表面処理工程
芯材としてのポリエチレン粉（平均粒子径Ｄ５０＝２０μｍ）を、水酸化ナトリウム水溶液で洗浄し、次いで、クロム酸、硫酸及びリン酸の混酸により表面粗化した後、フッ化スズ水溶液（１ｇ／Ｌ）に分散させ、撹拌し、濾過後、水洗し、更に硝酸銀水溶液（１ｇ／Ｌ）に分散させ、撹拌し、濾過後、水洗し、乾燥して、芯材の表面処理物Ａ４を得た。 Example 4
(1) Surface treatment step After the polyethylene powder (average particle diameter D 50 = 20 μm) as a core material is washed with an aqueous sodium hydroxide solution and then surface-roughened with a mixed acid of chromic acid, sulfuric acid and phosphoric acid, fluorine Disperse in tin chloride aqueous solution (1 g / L), stir, filter, wash with water, further disperse in silver nitrate aqueous solution (1 g / L), stir, filter, wash with water, dry, surface of core A processed product A4 was obtained.
（２）電着工程及び水洗工程
次いで、芯材の表面処理物Ａ４ １０ｇを、電解液水溶液１Ｌに加え、電極を設置し、マグネチックスターラーで撹拌しながら、以下の条件で、１５分間通電し、芯材の表面処理物Ａ４に亜酸化銅を電着させた。電着の進行につれて電解液水溶液のｐＨが上昇したが、塩酸（濃度：２％）を適宜添加して該水溶液のｐＨを９～１０の範囲に維持した。次いで、電解液水溶液を濾過し、濾過物を水洗後、グリセリン水溶液に分散後濾過、乾燥し、亜酸化銅被覆粒子Ｂ４ １４．６ｇを得た。亜酸化銅被覆粒子Ｂ４の真比重は１．２ｇ／ｃｍ3であった。
＜電解液水溶液＞
塩化ナトリウム：２５０ｇ／Ｌ（塩素イオン濃度１５２ｇ／Ｌ）
グリセリン ：１０ｇ／Ｌ
ｐＨ ：７
＜処理条件＞
電流密度 ：７Ａ／ｄｍ2
電解液水溶液の液温 ：３０℃
電極 ：陽極及び陰極のいずれも銅板 (2) Electrodeposition step and water washing step Next, 10 g of the surface treatment product A4 of the core material was added to 1 L of the aqueous electrolyte solution, an electrode was installed, and the mixture was stirred for 15 minutes under the following conditions while stirring with a magnetic stirrer. Then, cuprous oxide was electrodeposited on the surface treated product A4 of the core material. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition, but hydrochloric acid (concentration: 2%) was appropriately added to maintain the pH of the aqueous solution in the range of 9-10. Next, the aqueous electrolyte solution was filtered, and the filtrate was washed with water, dispersed in a glycerin aqueous solution, filtered and dried to obtain 14.6 g of cuprous oxide-coated particles B4. The true specific gravity of the cuprous oxide-coated particles B4 was 1.2 g / cm 3 .
<Electrolytic solution aqueous solution>
Sodium chloride: 250 g / L (chlorine ion concentration 152 g / L)
Glycerin: 10 g / L
pH: 7
<Processing conditions>
Current density: 7 A / dm 2
Liquid temperature of electrolyte aqueous solution: 30 ° C
Electrode: Copper plate for both anode and cathode
次いで、芯材の表面処理物Ａ４ １０ｇを、電解液水溶液１Ｌに加え、電極を設置し、マグネチックスターラーで撹拌しながら、以下の条件で、１５分間通電し、芯材の表面処理物Ａ４に亜酸化銅を電着させた。電着の進行につれて電解液水溶液のｐＨが上昇したが、塩酸（濃度：２％）を適宜添加して該水溶液のｐＨを９～１０の範囲に維持した。次いで、電解液水溶液を濾過し、濾過物を水洗後、グリセリン水溶液に分散後濾過、乾燥し、亜酸化銅被覆粒子Ｂ４ １４．６ｇを得た。亜酸化銅被覆粒子Ｂ４の真比重は１．２ｇ／ｃｍ3であった。
＜電解液水溶液＞
塩化ナトリウム：２５０ｇ／Ｌ（塩素イオン濃度１５２ｇ／Ｌ）
グリセリン ：１０ｇ／Ｌ
ｐＨ ：７
＜処理条件＞
電流密度 ：７Ａ／ｄｍ2
電解液水溶液の液温 ：３０℃
電極 ：陽極及び陰極のいずれも銅板 (2) Electrodeposition step and water washing step Next, 10 g of the surface treatment product A4 of the core material was added to 1 L of the aqueous electrolyte solution, an electrode was installed, and the mixture was stirred for 15 minutes under the following conditions while stirring with a magnetic stirrer. Then, cuprous oxide was electrodeposited on the surface treated product A4 of the core material. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition, but hydrochloric acid (concentration: 2%) was appropriately added to maintain the pH of the aqueous solution in the range of 9-10. Next, the aqueous electrolyte solution was filtered, and the filtrate was washed with water, dispersed in a glycerin aqueous solution, filtered and dried to obtain 14.6 g of cuprous oxide-coated particles B4. The true specific gravity of the cuprous oxide-coated particles B4 was 1.2 g / cm 3 .
<Electrolytic solution aqueous solution>
Sodium chloride: 250 g / L (chlorine ion concentration 152 g / L)
Glycerin: 10 g / L
pH: 7
<Processing conditions>
Current density: 7 A / dm 2
Liquid temperature of electrolyte aqueous solution: 30 ° C
Electrode: Copper plate for both anode and cathode
〔実施例５〕
（１）表面処理工程
芯材としての溶融シリカ粉（非晶質、平均粒子径Ｄ５０＝２０μｍ）を、水酸化ナトリウム水溶液によりアルカリ洗浄し、フッ化水素酸による表面粗化を施した後フッ化スズ（１ｇ／Ｌ）水溶液に分散させ、撹拌し、濾過後、水洗し、更に硝酸銀（１ｇ／Ｌ）水溶液に分散させ、撹拌し、濾過後、水洗し、乾燥して、芯材の表面処理物Ａ５を得た。 Example 5
(1) Surface treatment step Fused silica powder (amorphous, average particle diameter D 50 = 20 μm) as a core material is alkali-washed with an aqueous sodium hydroxide solution and subjected to surface roughening with hydrofluoric acid. Disperse in tin chloride (1 g / L) aqueous solution, stir, filter, wash with water, further disperse in silver nitrate (1 g / L) aqueous solution, stir, filter, wash with water, and dry, surface of core Processed product A5 was obtained.
（１）表面処理工程
芯材としての溶融シリカ粉（非晶質、平均粒子径Ｄ５０＝２０μｍ）を、水酸化ナトリウム水溶液によりアルカリ洗浄し、フッ化水素酸による表面粗化を施した後フッ化スズ（１ｇ／Ｌ）水溶液に分散させ、撹拌し、濾過後、水洗し、更に硝酸銀（１ｇ／Ｌ）水溶液に分散させ、撹拌し、濾過後、水洗し、乾燥して、芯材の表面処理物Ａ５を得た。 Example 5
(1) Surface treatment step Fused silica powder (amorphous, average particle diameter D 50 = 20 μm) as a core material is alkali-washed with an aqueous sodium hydroxide solution and subjected to surface roughening with hydrofluoric acid. Disperse in tin chloride (1 g / L) aqueous solution, stir, filter, wash with water, further disperse in silver nitrate (1 g / L) aqueous solution, stir, filter, wash with water, and dry, surface of core Processed product A5 was obtained.
（２）電着工程及び水洗工程
次いで、芯材の表面処理物Ａ５ １０ｇを電解液水溶液１Ｌに加え、電極を設置し、マグネチックスターラーで撹拌しながら、以下の条件で１５分間通電し、芯材の表面処理物Ａ５に亜酸化銅を電着させた。電着の進行につれて電解液水溶液のｐＨが上昇したが、塩酸（濃度：２％）を適宜添加して該水溶液のｐＨを９～１０の範囲に維持した。次いで、電解液水溶液を濾過し、濾過物を水洗後、グリセリン水溶液に分散後濾過、乾燥し、亜酸化銅被覆粒子Ｂ５ １４.３ｇを得た。亜酸化銅被覆粒子Ｂ５の真比重は２.８ｇ／cm3であった。 (2) Electrodeposition step and water washing step Next, 10 g of the surface treatment product A5 of the core material was added to 1 L of the electrolyte aqueous solution, an electrode was installed, and the mixture was energized for 15 minutes under the following conditions while stirring with a magnetic stirrer. Cuprous oxide was electrodeposited on the surface-treated material A5. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition, but hydrochloric acid (concentration: 2%) was appropriately added to maintain the pH of the aqueous solution in the range of 9-10. Next, the aqueous electrolyte solution was filtered, and the filtrate was washed with water, dispersed in a glycerin aqueous solution, filtered and dried to obtain 14.3 g of cuprous oxide-coated particles B5. The true specific gravity of the cuprous oxide-coated particle B5 was 2.8 g / cm 3 .
次いで、芯材の表面処理物Ａ５ １０ｇを電解液水溶液１Ｌに加え、電極を設置し、マグネチックスターラーで撹拌しながら、以下の条件で１５分間通電し、芯材の表面処理物Ａ５に亜酸化銅を電着させた。電着の進行につれて電解液水溶液のｐＨが上昇したが、塩酸（濃度：２％）を適宜添加して該水溶液のｐＨを９～１０の範囲に維持した。次いで、電解液水溶液を濾過し、濾過物を水洗後、グリセリン水溶液に分散後濾過、乾燥し、亜酸化銅被覆粒子Ｂ５ １４.３ｇを得た。亜酸化銅被覆粒子Ｂ５の真比重は２.８ｇ／cm3であった。 (2) Electrodeposition step and water washing step Next, 10 g of the surface treatment product A5 of the core material was added to 1 L of the electrolyte aqueous solution, an electrode was installed, and the mixture was energized for 15 minutes under the following conditions while stirring with a magnetic stirrer. Cuprous oxide was electrodeposited on the surface-treated material A5. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition, but hydrochloric acid (concentration: 2%) was appropriately added to maintain the pH of the aqueous solution in the range of 9-10. Next, the aqueous electrolyte solution was filtered, and the filtrate was washed with water, dispersed in a glycerin aqueous solution, filtered and dried to obtain 14.3 g of cuprous oxide-coated particles B5. The true specific gravity of the cuprous oxide-coated particle B5 was 2.8 g / cm 3 .
＜電解液水溶液＞
塩化ナトリウム：２５０ｇ／Ｌ（塩素イオン濃度１５２ｇ／Ｌ）
グリセリン ：１０ｇ／Ｌ
ｐＨ ：７
＜処理条件＞
電流密度 ：７Ａ／ｄｍ2
電解液水溶液の液温 ：３０℃
電極 ：陽極及び陰極のいずれも銅板 <Electrolytic solution aqueous solution>
Sodium chloride: 250 g / L (chlorine ion concentration 152 g / L)
Glycerin: 10 g / L
pH: 7
<Processing conditions>
Current density: 7 A / dm 2
Liquid temperature of electrolyte aqueous solution: 30 ° C
Electrode: Copper plate for both anode and cathode
塩化ナトリウム：２５０ｇ／Ｌ（塩素イオン濃度１５２ｇ／Ｌ）
グリセリン ：１０ｇ／Ｌ
ｐＨ ：７
＜処理条件＞
電流密度 ：７Ａ／ｄｍ2
電解液水溶液の液温 ：３０℃
電極 ：陽極及び陰極のいずれも銅板 <Electrolytic solution aqueous solution>
Sodium chloride: 250 g / L (chlorine ion concentration 152 g / L)
Glycerin: 10 g / L
pH: 7
<Processing conditions>
Current density: 7 A / dm 2
Liquid temperature of electrolyte aqueous solution: 30 ° C
Electrode: Copper plate for both anode and cathode
〔比較例１〕
電着工程において、電解液水溶液のｐＨを調整しなかった以外は、実施例１と同じ方法で亜酸化銅被覆粒子ｂ１を得た。電解液水溶液のｐＨは電着の進行とともに上昇し、１３を超えていた。得られた亜酸化銅被覆粒子ｂ１の真比重は２．６ｇ／ｃｍ3であった。 [Comparative Example 1]
In the electrodeposition step, cuprous oxide-coated particles b1 were obtained in the same manner as in Example 1 except that the pH of the aqueous electrolyte solution was not adjusted. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition and exceeded 13. The true specific gravity of the obtained cuprous oxide-coated particles b1 was 2.6 g / cm 3 .
電着工程において、電解液水溶液のｐＨを調整しなかった以外は、実施例１と同じ方法で亜酸化銅被覆粒子ｂ１を得た。電解液水溶液のｐＨは電着の進行とともに上昇し、１３を超えていた。得られた亜酸化銅被覆粒子ｂ１の真比重は２．６ｇ／ｃｍ3であった。 [Comparative Example 1]
In the electrodeposition step, cuprous oxide-coated particles b1 were obtained in the same manner as in Example 1 except that the pH of the aqueous electrolyte solution was not adjusted. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition and exceeded 13. The true specific gravity of the obtained cuprous oxide-coated particles b1 was 2.6 g / cm 3 .
〔比較例２〕
電着工程において、電解液水溶液のｐＨを調整しなかった以外は、実施例２と同じ方法で亜酸化銅被覆粒子ｂ２を得た。電解液水溶液のｐＨは電着の進行とともに上昇し、１３を超えていた。得られた亜酸化銅被覆粒子ｂ２の真比重は１．１ｇ／ｃｍ3であった。 [Comparative Example 2]
In the electrodeposition step, cuprous oxide-coated particles b2 were obtained in the same manner as in Example 2 except that the pH of the aqueous electrolyte solution was not adjusted. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition and exceeded 13. The true specific gravity of the obtained cuprous oxide-coated particles b2 was 1.1 g / cm 3 .
電着工程において、電解液水溶液のｐＨを調整しなかった以外は、実施例２と同じ方法で亜酸化銅被覆粒子ｂ２を得た。電解液水溶液のｐＨは電着の進行とともに上昇し、１３を超えていた。得られた亜酸化銅被覆粒子ｂ２の真比重は１．１ｇ／ｃｍ3であった。 [Comparative Example 2]
In the electrodeposition step, cuprous oxide-coated particles b2 were obtained in the same manner as in Example 2 except that the pH of the aqueous electrolyte solution was not adjusted. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition and exceeded 13. The true specific gravity of the obtained cuprous oxide-coated particles b2 was 1.1 g / cm 3 .
〔比較例３〕
電着工程において、電解液水溶液のｐＨを調整しなかった以外は、実施例３と同じ方法で亜酸化銅被覆粒子ｂ３を得た。電解液水溶液のｐＨは電着の進行とともに上昇し、１３を超えていた。得られた亜酸化銅被覆粒子ｂ３の真比重は３．１ｇ／ｃｍ3であった。 [Comparative Example 3]
In the electrodeposition step, cuprous oxide-coated particles b3 were obtained in the same manner as in Example 3 except that the pH of the aqueous electrolyte solution was not adjusted. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition and exceeded 13. The true specific gravity of the obtained cuprous oxide-coated particles b3 was 3.1 g / cm 3 .
電着工程において、電解液水溶液のｐＨを調整しなかった以外は、実施例３と同じ方法で亜酸化銅被覆粒子ｂ３を得た。電解液水溶液のｐＨは電着の進行とともに上昇し、１３を超えていた。得られた亜酸化銅被覆粒子ｂ３の真比重は３．１ｇ／ｃｍ3であった。 [Comparative Example 3]
In the electrodeposition step, cuprous oxide-coated particles b3 were obtained in the same manner as in Example 3 except that the pH of the aqueous electrolyte solution was not adjusted. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition and exceeded 13. The true specific gravity of the obtained cuprous oxide-coated particles b3 was 3.1 g / cm 3 .
〔比較例４〕
電着工程において、電解液水溶液のｐＨを調整しなかった以外は、実施例４と同じ方法で亜酸化銅被覆粒子ｂ４を得た。電解液水溶液のｐＨは電着の進行とともに上昇し、１３を超えていた。得られた亜酸化銅被覆粒子ｂ４の真比重は１．１ｇ／ｃｍ3であった。 [Comparative Example 4]
In the electrodeposition step, cuprous oxide-coated particles b4 were obtained in the same manner as in Example 4 except that the pH of the aqueous electrolyte solution was not adjusted. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition and exceeded 13. The true specific gravity of the obtained cuprous oxide-coated particles b4 was 1.1 g / cm 3 .
電着工程において、電解液水溶液のｐＨを調整しなかった以外は、実施例４と同じ方法で亜酸化銅被覆粒子ｂ４を得た。電解液水溶液のｐＨは電着の進行とともに上昇し、１３を超えていた。得られた亜酸化銅被覆粒子ｂ４の真比重は１．１ｇ／ｃｍ3であった。 [Comparative Example 4]
In the electrodeposition step, cuprous oxide-coated particles b4 were obtained in the same manner as in Example 4 except that the pH of the aqueous electrolyte solution was not adjusted. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition and exceeded 13. The true specific gravity of the obtained cuprous oxide-coated particles b4 was 1.1 g / cm 3 .
〔比較例５〕
電着工程において、電解液水溶液のｐＨを調整しなかった以外は、実施例５と同じ方法で亜酸化銅被覆粒子ｂ５を得た。電解液水溶液のｐＨは電着の進行とともに上昇し、１３を超えていた。得られた亜酸化銅被覆粒子ｂ５の真比重は２．７ｇ／ｃｍ3であった。 [Comparative Example 5]
In the electrodeposition step, cuprous oxide-coated particles b5 were obtained in the same manner as in Example 5 except that the pH of the aqueous electrolyte solution was not adjusted. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition and exceeded 13. The true specific gravity of the obtained cuprous oxide-coated particles b5 was 2.7 g / cm 3 .
電着工程において、電解液水溶液のｐＨを調整しなかった以外は、実施例５と同じ方法で亜酸化銅被覆粒子ｂ５を得た。電解液水溶液のｐＨは電着の進行とともに上昇し、１３を超えていた。得られた亜酸化銅被覆粒子ｂ５の真比重は２．７ｇ／ｃｍ3であった。 [Comparative Example 5]
In the electrodeposition step, cuprous oxide-coated particles b5 were obtained in the same manner as in Example 5 except that the pH of the aqueous electrolyte solution was not adjusted. The pH of the aqueous electrolyte solution increased with the progress of electrodeposition and exceeded 13. The true specific gravity of the obtained cuprous oxide-coated particles b5 was 2.7 g / cm 3 .
〔評価〕
実施例１で得られた亜酸化銅被覆粒子の走査型電子顕微鏡像を図１に、比較例２で得られた亜酸化銅被覆粒子の走査型電子顕微鏡像を図２に示す。図１から明らかなように、実施例１で得られた亜酸化銅被覆粒子では、八面体状の亜酸化銅粒子の集合体からなる緻密な層が、芯材の表面を完全被覆していることが判る。観察対象とした亜酸化銅粒子１００個に対して９０個以上の粒子が八面体形状であった。これに対して、図２から明らかなように、比較例１で得られた亜酸化銅被覆粒子は、不定形の亜酸化銅粒子の集合体からなる層が、芯材の表面を被覆していた。また、図示していないが、実施例２～５で得られた亜酸化銅被覆粒子においても、実施例１の亜酸化銅被覆粒子と同様に、八面体状の亜酸化銅粒子の集合体からなる緻密な層が、芯材の表面を完全被覆していることが確認された。これらの実施例においては、観察対象とした亜酸化銅粒子１００個に対して９０個以上の粒子が八面体形状であった。比較例２～５で得られた亜酸化銅粒子は不定形となっていた。 [Evaluation]
A scanning electron microscope image of the cuprous oxide-coated particles obtained in Example 1 is shown in FIG. 1, and a scanning electron microscope image of the cuprous oxide-coated particles obtained in Comparative Example 2 is shown in FIG. As is apparent from FIG. 1, in the cuprous oxide-coated particles obtained in Example 1, a dense layer made of an aggregate of octahedral cuprous oxide particles completely covers the surface of the core material. I understand that. More than 90 particles were octahedral with respect to 100 cuprous oxide particles to be observed. On the other hand, as is apparent from FIG. 2, the cuprous oxide-coated particles obtained in Comparative Example 1 have a layer made of an aggregate of amorphous cuprous oxide particles covering the surface of the core material. It was. In addition, although not shown, the cuprous oxide-coated particles obtained in Examples 2 to 5 are also formed from an aggregate of octahedral cuprous oxide particles, similar to the cuprous oxide-coated particles of Example 1. It was confirmed that this dense layer completely covered the surface of the core material. In these examples, 90 or more particles were octahedral with respect to 100 cuprous oxide particles to be observed. The cuprous oxide particles obtained in Comparative Examples 2 to 5 were amorphous.
実施例１で得られた亜酸化銅被覆粒子の走査型電子顕微鏡像を図１に、比較例２で得られた亜酸化銅被覆粒子の走査型電子顕微鏡像を図２に示す。図１から明らかなように、実施例１で得られた亜酸化銅被覆粒子では、八面体状の亜酸化銅粒子の集合体からなる緻密な層が、芯材の表面を完全被覆していることが判る。観察対象とした亜酸化銅粒子１００個に対して９０個以上の粒子が八面体形状であった。これに対して、図２から明らかなように、比較例１で得られた亜酸化銅被覆粒子は、不定形の亜酸化銅粒子の集合体からなる層が、芯材の表面を被覆していた。また、図示していないが、実施例２～５で得られた亜酸化銅被覆粒子においても、実施例１の亜酸化銅被覆粒子と同様に、八面体状の亜酸化銅粒子の集合体からなる緻密な層が、芯材の表面を完全被覆していることが確認された。これらの実施例においては、観察対象とした亜酸化銅粒子１００個に対して９０個以上の粒子が八面体形状であった。比較例２～５で得られた亜酸化銅粒子は不定形となっていた。 [Evaluation]
A scanning electron microscope image of the cuprous oxide-coated particles obtained in Example 1 is shown in FIG. 1, and a scanning electron microscope image of the cuprous oxide-coated particles obtained in Comparative Example 2 is shown in FIG. As is apparent from FIG. 1, in the cuprous oxide-coated particles obtained in Example 1, a dense layer made of an aggregate of octahedral cuprous oxide particles completely covers the surface of the core material. I understand that. More than 90 particles were octahedral with respect to 100 cuprous oxide particles to be observed. On the other hand, as is apparent from FIG. 2, the cuprous oxide-coated particles obtained in Comparative Example 1 have a layer made of an aggregate of amorphous cuprous oxide particles covering the surface of the core material. It was. In addition, although not shown, the cuprous oxide-coated particles obtained in Examples 2 to 5 are also formed from an aggregate of octahedral cuprous oxide particles, similar to the cuprous oxide-coated particles of Example 1. It was confirmed that this dense layer completely covered the surface of the core material. In these examples, 90 or more particles were octahedral with respect to 100 cuprous oxide particles to be observed. The cuprous oxide particles obtained in Comparative Examples 2 to 5 were amorphous.
芯材と亜酸化銅との質量比（芯材／亜酸化銅）は、実施例１においては５０／５０であったのに対し、比較例１においては７６／２４であり、比較例１では亜酸化銅の付着量が少なくことが判る。そのことに起因して、比較例１の亜酸化銅被覆粒子の真比重は、実施例１の亜酸化銅被覆粒子のそれよりも低くなったものと考えられる。実施例２～５及び比較例２～５の亜酸化銅被覆粒子についても同様の測定を行った。その結果を以下の表１に示す。
The mass ratio of the core material and cuprous oxide (core material / cuprous oxide) was 50/50 in Example 1, whereas it was 76/24 in Comparative Example 1, and in Comparative Example 1, It can be seen that the amount of cuprous oxide attached is small. As a result, the true specific gravity of the cuprous oxide-coated particles of Comparative Example 1 is considered to be lower than that of the cuprous oxide-coated particles of Example 1. The same measurement was performed on the cuprous oxide-coated particles of Examples 2 to 5 and Comparative Examples 2 to 5. The results are shown in Table 1 below.
また、実施例１における亜酸化銅粒子の層における八面体状の粒子の粒径を上述の方法で測定したところ０.７μｍであった。比較例１における亜酸化銅粒子の粒径は、該粒子が不定形であるため測定できなかった。実施例２～５及び比較例２～５の亜酸化銅被覆粒子についても同様の測定を行った。その結果を以下の表１に示す。
Further, the particle size of the octahedral particles in the cuprous oxide particle layer in Example 1 was measured by the above-mentioned method, and was 0.7 μm. The particle size of the cuprous oxide particles in Comparative Example 1 could not be measured because the particles were amorphous. The same measurement was performed on the cuprous oxide-coated particles of Examples 2 to 5 and Comparative Examples 2 to 5. The results are shown in Table 1 below.
更に、実施例１～５及び比較例１～５で得られた亜酸化銅被覆粒子における亜酸化銅の層の密着性を以下の方法で評価した。
（１）亜酸化銅被覆粒子２.２ｇ、１ｍｍΦのジルコニアビーズ９０ｇ及びトルエン１０ｍｌを、容器に入れる。
（２）撹拌装置で、１０分間撹拌する。
（３）撹拌後、ふるいで、亜酸化銅被覆粒子とジルコニアビーズとを分ける。
（４）分けた亜酸化銅被覆粒子を漏斗で濾過する。
（５）亜酸化銅被覆粒子を自然乾燥する。
（６）走査型電子顕微鏡（５００倍、視野に５０個程度の粒子が入る倍率を選択する。）により、芯材からの亜酸化銅粒子の剥離状態を観察する。
（７）無作為に１０視野を観察し、各視野中の剥離粒子数を数え、平均値を求める。
以上の方法で測定された剥離粒子数を以下の表１示す。剥離粒子数は、その数が小さいほど、亜酸化銅の層の密着性が高いことを意味する。 Further, the adhesion of the cuprous oxide layer in the cuprous oxide-coated particles obtained in Examples 1 to 5 and Comparative Examples 1 to 5 was evaluated by the following method.
(1) Cuprous oxide-coated particles (2.2 g), 1 mmφ zirconia beads (90 g) and toluene (10 ml) are placed in a container.
(2) Stir with a stirrer for 10 minutes.
(3) After stirring, the cuprous oxide-coated particles and zirconia beads are separated with a sieve.
(4) Filter the separated cuprous oxide-coated particles with a funnel.
(5) The cuprous oxide-coated particles are naturally dried.
(6) The peeling state of the cuprous oxide particles from the core material is observed with a scanning electron microscope (500 times, and a magnification at which about 50 particles enter the visual field is selected).
(7) Observe 10 visual fields at random, count the number of exfoliated particles in each visual field, and determine the average value.
The number of peeled particles measured by the above method is shown in Table 1 below. The smaller the number, the higher the adhesion of the cuprous oxide layer.
（１）亜酸化銅被覆粒子２.２ｇ、１ｍｍΦのジルコニアビーズ９０ｇ及びトルエン１０ｍｌを、容器に入れる。
（２）撹拌装置で、１０分間撹拌する。
（３）撹拌後、ふるいで、亜酸化銅被覆粒子とジルコニアビーズとを分ける。
（４）分けた亜酸化銅被覆粒子を漏斗で濾過する。
（５）亜酸化銅被覆粒子を自然乾燥する。
（６）走査型電子顕微鏡（５００倍、視野に５０個程度の粒子が入る倍率を選択する。）により、芯材からの亜酸化銅粒子の剥離状態を観察する。
（７）無作為に１０視野を観察し、各視野中の剥離粒子数を数え、平均値を求める。
以上の方法で測定された剥離粒子数を以下の表１示す。剥離粒子数は、その数が小さいほど、亜酸化銅の層の密着性が高いことを意味する。 Further, the adhesion of the cuprous oxide layer in the cuprous oxide-coated particles obtained in Examples 1 to 5 and Comparative Examples 1 to 5 was evaluated by the following method.
(1) Cuprous oxide-coated particles (2.2 g), 1 mmφ zirconia beads (90 g) and toluene (10 ml) are placed in a container.
(2) Stir with a stirrer for 10 minutes.
(3) After stirring, the cuprous oxide-coated particles and zirconia beads are separated with a sieve.
(4) Filter the separated cuprous oxide-coated particles with a funnel.
(5) The cuprous oxide-coated particles are naturally dried.
(6) The peeling state of the cuprous oxide particles from the core material is observed with a scanning electron microscope (500 times, and a magnification at which about 50 particles enter the visual field is selected).
(7) Observe 10 visual fields at random, count the number of exfoliated particles in each visual field, and determine the average value.
The number of peeled particles measured by the above method is shown in Table 1 below. The smaller the number, the higher the adhesion of the cuprous oxide layer.
更に、実施例１～５及び比較例１～５で得られた亜酸化銅被覆粒子を顔料として用い、以下の処方の防汚塗料を調製した。この防汚塗料について、調製直後の粘度及び５０℃で３６日間保存後の粘度をストーマー粘度計によって測定した。その結果を以下の表１に示す。
Furthermore, using the cuprous oxide-coated particles obtained in Examples 1 to 5 and Comparative Examples 1 to 5 as pigments, antifouling paints having the following formulation were prepared. About this antifouling paint, the viscosity immediately after preparation and the viscosity after 36-day storage at 50 degreeC were measured with the Stormer viscometer. The results are shown in Table 1 below.
〔防汚塗料の処方〕
・亜酸化銅被覆粉体 １０％
・キシレン ２５％
・メタノール ５％
・４０％ウレタン樹脂キシレン溶液 ６０％ [Prescription of antifouling paint]
・ Copper oxide coated powder 10%
・ Xylene 25%
・ Methanol 5%
・ 40% urethane resin xylene solution 60%
・亜酸化銅被覆粉体 １０％
・キシレン ２５％
・メタノール ５％
・４０％ウレタン樹脂キシレン溶液 ６０％ [Prescription of antifouling paint]
・ Copper oxide coated powder 10%
・ Xylene 25%
・ Methanol 5%
・ 40% urethane resin xylene solution 60%
この結果、実施例１～５で得られた亜酸化銅被覆粒子は剥離粒子数が１以下であり、比較例１～５で得られた亜酸化銅被覆粒子に比べて剥離粒子数が少ないことから、亜酸化銅の層の密着性に優れていることが分かる。また、実施例１～５で得られた亜酸化銅被覆粒子を含む防汚塗料は調製直後から３６日間保存後の粘度上昇が抑えられ、比較例１～５で得られた亜酸化銅被覆粒子を含む防汚塗料に比べると塗料安定性に優れていることが分かる。
As a result, the cuprous oxide-coated particles obtained in Examples 1 to 5 had a number of exfoliated particles of 1 or less, and the number of exfoliated particles was smaller than the cuprous oxide-coated particles obtained in Comparative Examples 1 to 5. Thus, it can be seen that the adhesion of the cuprous oxide layer is excellent. In addition, the antifouling paint containing the cuprous oxide-coated particles obtained in Examples 1 to 5 suppressed the increase in viscosity after storage for 36 days immediately after preparation, and the cuprous oxide-coated particles obtained in Comparative Examples 1 to 5 It can be seen that the paint stability is superior compared to the antifouling paint containing.
Claims (8)
- 芯材の表面が亜酸化銅の層で被覆されてなる亜酸化銅被覆粒子において、
前記亜酸化銅の層は、前記芯材の表面を完全被覆しているとともに、八面体状の亜酸化銅の粒子の集合体から構成されていることを特徴とする亜酸化銅被覆粒子。 In the cuprous oxide-coated particles in which the surface of the core material is coated with a cuprous oxide layer,
The cuprous oxide-coated particle is characterized in that the cuprous oxide layer completely covers the surface of the core material and is composed of an aggregate of octahedral cuprous oxide particles. - 前記芯材のＤ50が０．５～１００μｍである請求項１記載の亜酸化銅被覆粒子。 The cuprous oxide-coated particles according to claim 1, wherein D 50 of the core material is 0.5 to 100 µm.
- 前記芯材が、珪酸含有無機化合物である請求項１又は２記載の亜酸化銅被覆粒子。 The cuprous oxide-coated particles according to claim 1 or 2, wherein the core material is a silicic acid-containing inorganic compound.
- 前記芯材が、アルカリ土類金属化合物である請求項１又は２記載の亜酸化銅被覆粒子。 The cuprous oxide-coated particles according to claim 1 or 2, wherein the core material is an alkaline earth metal compound.
- 前記芯材が、有機化合物である請求項１又は２記載の亜酸化銅被覆粒子。 The cuprous oxide-coated particles according to claim 1 or 2, wherein the core material is an organic compound.
- 防汚塗料用の顔料として用いられる請求項１ないし５のいずれかに記載の亜酸化銅被覆粒子。 The cuprous oxide-coated particles according to any one of claims 1 to 5, which are used as a pigment for an antifouling paint.
- 請求項１ないし６のいずれかに記載の亜酸化銅被覆粒子及び被膜形成性重合体を含むことを特徴とする防汚塗料。 An antifouling paint comprising the cuprous oxide-coated particles according to any one of claims 1 to 6 and a film-forming polymer.
- 請求項１記載の亜酸化銅被覆粒子の製造方法であって、
芯材を、第一スズ塩の水溶液、銀塩の水溶液及びパラジウム塩の水溶液のいずれか１種又は２種以上の表面処理水溶液に接触させて、芯材の表面処理物を得る表面処理工程と、
前記芯材の表面処理物を、電解質及び酸化防止剤を含有する電解液水溶液に分散させ、金属銅を陽極として用いて電解を行い、該芯材の表面処理物の表面に亜酸化銅を電着させて、亜酸化銅被覆粒子を得る電着工程とを有し、
電着工程における前記電解液水溶液のｐＨを７～１３に維持して亜酸化銅の電着を行うことを特徴とする亜酸化銅被覆粒子の製造方法。 A method for producing cuprous oxide-coated particles according to claim 1,
A surface treatment step of bringing the core material into contact with one or more surface treatment aqueous solutions of an aqueous solution of stannous salt, an aqueous solution of silver salt, and an aqueous solution of palladium salt to obtain a surface treatment product of the core material; ,
The surface treatment product of the core material is dispersed in an aqueous electrolyte solution containing an electrolyte and an antioxidant, electrolysis is performed using metallic copper as an anode, and cuprous oxide is charged on the surface of the surface treatment product of the core material. And having an electrodeposition step of obtaining cuprous oxide-coated particles,
A method for producing cuprous oxide-coated particles, wherein the electrodeposition of cuprous oxide is performed while maintaining the pH of the aqueous electrolyte solution in the electrodeposition step at 7 to 13.
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| SG2012004263A SG178066A1 (en) | 2009-07-22 | 2010-07-21 | Particles coated with cuprous oxide, method for producing same, and antifouling coating material containing the particles coated with cuprous oxide |
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| JP2009171493 | 2009-07-22 | ||
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| JP2010159826A JP2011042559A (en) | 2009-07-22 | 2010-07-14 | Particle coated with cuprous oxide and method for producing the same, and antifouling coating material containing the particle coated with cuprous oxide |
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| JP (1) | JP2011042559A (en) |
| KR (1) | KR20120041209A (en) |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250499A (en) * | 2011-05-16 | 2011-11-23 | 大连海事大学 | Preparation method of cuprous oxide coated and treated by rosin |
| DE102012103903A1 (en) | 2012-05-03 | 2013-11-07 | Eckart Gmbh | Flaky effect pigment comprising a copper-containing coating, process for its preparation and use thereof |
| WO2013174250A1 (en) * | 2012-05-21 | 2013-11-28 | 广东先导稀材股份有限公司 | Composite of cuprous oxide surface-coated with copper oxide and preparation method therefor |
| CN105536791A (en) * | 2015-12-30 | 2016-05-04 | 河北工程大学 | Preparation method of octahedral cuprous oxide catalyst for synthesizing methyl chlorosilane monomers |
| CN109761263A (en) * | 2019-03-15 | 2019-05-17 | 重庆大学 | Preparation method of cuprous oxide crystal with controllable morphology |
| CN115229200A (en) * | 2022-07-26 | 2022-10-25 | 西安培华学院 | Preparation method of cubic porous silver micron material |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6487159B2 (en) * | 2014-07-14 | 2019-03-20 | 中国塗料株式会社 | Antifouling paint composition, antifouling film, method for producing antifouling film and antifouling substrate |
| KR102168357B1 (en) | 2016-03-28 | 2020-10-22 | 도요세이칸 그룹 홀딩스 가부시키가이샤 | Dispersion and its manufacturing method, and copper compound particles |
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| JPS6164763A (en) * | 1984-09-06 | 1986-04-03 | Chugoku Toryo Kk | Cuprous oxide composition |
| JPH01213368A (en) * | 1988-02-02 | 1989-08-28 | Nippon Mining Co Ltd | Composite pigment for antifouling paint and its manufacturing method |
| JPH0393623A (en) * | 1989-09-01 | 1991-04-18 | Nippon Mining Co Ltd | Production of cuprous oxide |
| JPH03193618A (en) * | 1989-12-21 | 1991-08-23 | Nippon Mining Co Ltd | Continuous production of composite powder |
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2010
- 2010-07-14 JP JP2010159826A patent/JP2011042559A/en active Pending
- 2010-07-21 KR KR1020127002999A patent/KR20120041209A/en not_active Withdrawn
- 2010-07-21 SG SG2012004263A patent/SG178066A1/en unknown
- 2010-07-21 WO PCT/JP2010/062247 patent/WO2011010663A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6164763A (en) * | 1984-09-06 | 1986-04-03 | Chugoku Toryo Kk | Cuprous oxide composition |
| JPH01213368A (en) * | 1988-02-02 | 1989-08-28 | Nippon Mining Co Ltd | Composite pigment for antifouling paint and its manufacturing method |
| JPH0393623A (en) * | 1989-09-01 | 1991-04-18 | Nippon Mining Co Ltd | Production of cuprous oxide |
| JPH03193618A (en) * | 1989-12-21 | 1991-08-23 | Nippon Mining Co Ltd | Continuous production of composite powder |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250499A (en) * | 2011-05-16 | 2011-11-23 | 大连海事大学 | Preparation method of cuprous oxide coated and treated by rosin |
| DE102012103903A1 (en) | 2012-05-03 | 2013-11-07 | Eckart Gmbh | Flaky effect pigment comprising a copper-containing coating, process for its preparation and use thereof |
| US9127165B2 (en) | 2012-05-03 | 2015-09-08 | Eckart Gmbh | Plate-shaped effect pigment comprising a copper-containing coating, method for the production thereof, and use thereof |
| WO2013174250A1 (en) * | 2012-05-21 | 2013-11-28 | 广东先导稀材股份有限公司 | Composite of cuprous oxide surface-coated with copper oxide and preparation method therefor |
| CN105536791A (en) * | 2015-12-30 | 2016-05-04 | 河北工程大学 | Preparation method of octahedral cuprous oxide catalyst for synthesizing methyl chlorosilane monomers |
| CN105536791B (en) * | 2015-12-30 | 2018-06-29 | 河北工程大学 | The preparation method of the octahedra cuprous oxide catalysis agent of synthesizing methyl-chloro-silane monomer |
| CN109761263A (en) * | 2019-03-15 | 2019-05-17 | 重庆大学 | Preparation method of cuprous oxide crystal with controllable morphology |
| CN109761263B (en) * | 2019-03-15 | 2021-05-14 | 重庆大学 | Preparation method of cuprous oxide crystal with controllable shape |
| CN115229200A (en) * | 2022-07-26 | 2022-10-25 | 西安培华学院 | Preparation method of cubic porous silver micron material |
| CN115229200B (en) * | 2022-07-26 | 2024-04-09 | 西安培华学院 | Preparation method of cube-shaped porous silver micrometer material |
Also Published As
| Publication number | Publication date |
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| KR20120041209A (en) | 2012-04-30 |
| JP2011042559A (en) | 2011-03-03 |
| SG178066A1 (en) | 2012-03-29 |
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