WO2016017792A1 - 含触媒金属シリコンオリゴマー、その製造方法および含触媒金属シリコンオリゴマーの用途 - Google Patents
含触媒金属シリコンオリゴマー、その製造方法および含触媒金属シリコンオリゴマーの用途 Download PDFInfo
- Publication number
- WO2016017792A1 WO2016017792A1 PCT/JP2015/071752 JP2015071752W WO2016017792A1 WO 2016017792 A1 WO2016017792 A1 WO 2016017792A1 JP 2015071752 W JP2015071752 W JP 2015071752W WO 2016017792 A1 WO2016017792 A1 WO 2016017792A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- silicon oligomer
- containing metal
- metal silicon
- plating
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 99
- 239000002184 metal Substances 0.000 title claims abstract description 99
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 97
- 239000010703 silicon Substances 0.000 title claims abstract description 97
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 68
- 238000007747 plating Methods 0.000 claims abstract description 48
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 82
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 67
- 238000006482 condensation reaction Methods 0.000 claims description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- 229910052763 palladium Inorganic materials 0.000 claims description 29
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 230000003197 catalytic effect Effects 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims 1
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 53
- 239000011521 glass Substances 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 15
- 239000010410 layer Substances 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000002356 single layer Substances 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 7
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- -1 III) Inorganic materials 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007772 electroless plating Methods 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 description 2
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- RUOPINZRYMFPBF-UHFFFAOYSA-N pentane-1,3-diol Chemical compound CCC(O)CCO RUOPINZRYMFPBF-UHFFFAOYSA-N 0.000 description 1
- XLMFDCKSFJWJTP-UHFFFAOYSA-N pentane-2,3-diol Chemical compound CCC(O)C(C)O XLMFDCKSFJWJTP-UHFFFAOYSA-N 0.000 description 1
- GTCCGKPBSJZVRZ-UHFFFAOYSA-N pentane-2,4-diol Chemical compound CC(O)CC(C)O GTCCGKPBSJZVRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/04—Esters of silicic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
Definitions
- the present invention relates to a catalyst-containing metal silicon oligomer capable of imparting autocatalytic properties and conductivity to a substrate, a production method thereof, and uses of the catalyst-containing metal silicon oligomer.
- ⁇ ⁇ ⁇ Plating is generally performed for the purpose of improving the decorative properties of the base metal and improving the corrosion resistance.
- etching with an aqueous solution containing a cationic polymer and a bifluoride salt is also carried out as a pretreatment (Patent Document 1), but this still cannot be applied to all difficult-to-platable materials.
- an object of the present invention is to provide a new pretreatment technique that enables plating regardless of the type of substrate.
- the present inventors have conducted a condensation reaction between an alkoxysilane and a polyhydric alcohol having a hydroxy group bonded to a specific position in the presence of a catalytic metal.
- a condensation reaction between an alkoxysilane and a polyhydric alcohol having a hydroxy group bonded to a specific position in the presence of a catalytic metal.
- the present invention includes tetraalkoxysilane, A polyhydric alcohol having a hydroxy group bonded to at least the n, n + 1 position or the n, n + 2 position (where n is an integer of 1 or more), In the presence of catalytic metal, It is a catalyst-containing metal silicon oligomer obtained by a condensation reaction.
- the present invention also includes tetraalkoxysilane, A polyhydric alcohol having a hydroxy group bonded to at least the n, n + 1 position or the n, n + 2 position (where n is an integer of 1 or more), In the presence of catalytic metal, It is a method for producing a catalyst-containing metal silicon oligomer characterized by carrying out a condensation reaction.
- the present invention is a coating agent characterized by containing the above catalyst-containing metal silicon oligomer.
- the present invention is a method for plating a substrate, characterized in that after the substrate is treated with the above coating agent, the catalytic metal is activated, and then plated.
- the catalyst-containing metal silicon oligomer of the present invention has a catalyst metal incorporated in its structure, it can be provided with autocatalytic properties and conductivity based on the catalyst metal by coating the substrate.
- the catalyst-containing metal silicon oligomer of the present invention can be coated without chemically or physically roughening the surface of the substrate before coating, which has been essential in the past.
- the type of substrate to be coated is not limited.
- the catalyst-containing metal silicon oligomer can easily be plated on various substrates.
- the catalyst-containing metal silicon oligomer of the present invention does not cause problems such as gelation, which has been a problem with conventional silicon oligomers, it can be stably stored for more than one year after production.
- the catalyst-containing metal silicon oligomer of the present invention is Tetraalkoxysilane, A polyhydric alcohol having a hydroxy group bonded to at least the n, n + 1 position or the n, n + 2 position (where n is an integer of 1 or more), In the presence of catalytic metal, It is obtained by a condensation reaction.
- the tetraalkoxysilane used above is not particularly limited, and examples thereof include tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane. Among these, tetraethoxysilane is preferable. These tetraalkoxysilanes may be used alone or in combination of two or more.
- the polyhydric alcohol having a hydroxy group bonded to at least the n, n + 1 position or n, n + 2 position (where n is an integer of 1 or more) used in the above is not particularly limited.
- n is an integer of 1 to 3
- dihydric to tetrahydric alcohols preferably dihydric to trihydric alcohols where n is an integer of 1 to 2.
- polyhydric alcohols include, for example, ethylene glycol, 1,2-propanediol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 2-methyl-1,3-propylene glycol, 1,2-pentylene glycol, 1,3-pentylene glycol, 2,3-pentylene glycol, dihydric alcohols such as 2,4-pentylene glycol, glycerin, etc. And tetrahydric alcohols such as erythritol. Of these polyhydric alcohols, dihydric alcohols are preferred, ethylene glycol and / or 1,3-propylene glycol are more preferred, and ethylene glycol is particularly preferred. These polyhydric alcohols can be used alone or in combination of two or more.
- the catalyst metal used above is not a metal having a catalytic action for the condensation reaction of tetraalkoxysilane and polyhydric alcohol, but a metal having an autocatalytic action for the deposition reaction of plating described later. Therefore, it is different from the metal catalyst referred to in WO2014 / 20785 and WO2014 / 207886.
- Examples of such catalytic metals include iron, nickel, cobalt, copper, palladium, silver, gold, platinum, and the like.
- iron, nickel, cobalt, copper, and palladium are preferable, iron, nickel, copper, and palladium are more preferable, and palladium is particularly preferable.
- a method for subjecting the above tetraalkoxysilane and polyhydric alcohol to a condensation reaction in the presence of a catalytic metal is not particularly limited.
- 0.01 to 20 g / kg of catalytic metal is added to the polyhydric alcohol, preferably After adding and dissolving at 0.1 to 10 g / kg, the mixture is heated to the reaction temperature while stirring, and tetraalkoxysilane is further added and reacted.
- the reaction temperature is 25 to 150 ° C., preferably 30 to 70 ° C.
- the reaction time is 30 minutes to 8 hours, preferably 2 hours to 4 hours.
- the tetraalkoxysilane and the polyhydric alcohol are separated into two layers before the condensation reaction, but when the reaction is completed, one layer is formed. Also good.
- the catalyst-containing metal silicon oligomer of the present invention is a product obtained by condensation reaction of an alkoxy group of tetraalkoxysilane and one or two of n, n + 1-position or n, n + 2-position hydroxy groups present in a polyhydric alcohol.
- it has the following partial structures (a) to (d).
- the catalyst metal exists between oxygen atoms, and is presumed to be stabilized by forming a 5-membered ring structure or a 6-membered ring structure having the catalyst metal as a vertex. . Therefore, the catalyst-containing metal silicon oligomer of the present invention does not show any catalyst metal precipitation even after one year has passed after the production.
- Such a catalyst-containing metal silicon oligomer of the present invention can be identified by known methods such as NMR such as 1 HNMR and 29 SiNMR, IR, and MASS. Specifically for NMR, the alcohol produced by the condensation reaction of tetraalkoxysilane and polyhydric alcohol is confirmed by 1 HNMR, and further, the number of silicon in the catalyst-containing metal silicon oligomer is confirmed by 29 SiNMR, The catalyst-containing metal silicon oligomer of the present invention can be identified. In addition, the catalytic metal is taken into the silicon oligomer can be confirmed by the fact that no precipitation of the catalytic metal is observed after a certain period of time has elapsed after the silicon oligomer has been generated, for example, after one year.
- the catalyst-containing metal silicon oligomer of the present invention can be treated on the surface of the base material as a coating agent in the same manner as conventional silicon oligomers.
- the catalyst-containing metal silicon oligomer of the present invention has a catalytic metal incorporated in its structure. Therefore, after the substrate is treated with a coating agent, an activation treatment is performed, whereby the substrate is self-catalytic and conductive. Sex can be imparted.
- the coating agent may contain, for example, a solvent added to a conventionally known coating agent, a resin for improving wettability to a substrate, and the like.
- a coating agent can be prepared by appropriately stirring and mixing the above components.
- the solvent added to the coating agent is not particularly limited, and examples thereof include water, isopropyl alcohol, and ethyl cellosolve.
- the catalyst-containing metal silicon oligomer of the present invention can be stably stored even in the presence of water when diluted with a glycol-based solvent such as polyethylene glycol or ethyl cellosolve.
- a glycol-based solvent such as polyethylene glycol or ethyl cellosolve.
- polyethylene glycol 200 to 1000, preferably polyethylene glycol 200, as a glycol solvent it can be stably stored for a long time even in the presence of moisture.
- the coating agent may be blended with a colorant, a friction coefficient adjusting agent, a film thickener, and other additives that impart functionality as long as the effects of the present invention are not impaired.
- the said coating agent does not specifically limit as a base material processed by the said coating agent, If the said coating agent is utilized, it will be difficult to provide autocatalytic property and electroconductivity by the conventional technology, from the relationship of an ionization tendency etc. Self-catalytic properties and electrical conductivity can be imparted to difficult-to-platable substrates such as metals that cannot be plated, such as magnesium, metals that are not self-catalytic, wood, cloth, glass, ceramics, plastics, and the like. Therefore, it is preferable to use the coating agent for the aforementioned difficult-to-platable substrate. Further, among the above base materials, those having oxygen or hydroxy groups on the surface of the base material, for example, ABS, glass, etc., will have high adhesion.
- the substrate may be treated with the coating agent in the same manner as a conventionally known coating agent.
- the substrate may be treated by an immersion method such as a dip-and-spin method or a spray method such as a spray coating method. That's fine.
- a picture or a circuit may be formed with a coating agent by masking or an inkjet method.
- the thickness of the coating agent on the substrate is not particularly limited as long as the substrate is covered. After the treatment, it may be dried as it is or with warm air.
- an activation treatment is performed to reduce the catalytic metal.
- This activation treatment may be performed by appropriately combining heat treatment and chemical reduction treatment according to the characteristics of the substrate. For example, if it is a base material which does not have a problem even if it heats to 100 degreeC or more, such as glass and a ceramic, what is necessary is just to heat-process at 100 degreeC or more.
- heat treatment may be performed at less than 100 ° C., preferably 50 to 100 ° C., and then chemical reduction treatment may be performed.
- the heat treatment is not particularly limited.
- the temperature may be maintained for about 10 minutes to 2 hours in an oven, an electric furnace, or the like.
- the atmosphere of the heat treatment is not particularly limited and may be air. After the heat treatment, it may be allowed to cool.
- the chemical reduction treatment is not particularly limited, and may be immersed in an aqueous solution containing a reducing agent for about 1 to 3 minutes, for example.
- a reducing agent examples include hypophosphorous acid, dimethylamine borane, formaldehyde, sodium borohydride, hydrazine and the like. These reducing agents can be used alone or in combination of two or more. What is necessary is just to wash with water, dry, etc. after a chemical reduction process.
- the base material subjected to the above chemical reduction treatment is given autocatalytic properties, it can be subsequently plated.
- the type of plating is not particularly limited, and any of electroplating, electroless plating and the like may be used.
- the type of metal to be plated is not particularly limited, and may be any of nickel, copper, and the like.
- the coating agent containing the catalyst-containing metal silicon oligomer of the present invention is used, plating can be performed regardless of the type of substrate. And the plating product obtained consists of the layer of the metal which plated, the layer of the coating agent containing the catalyst-containing metal silicon oligomer of this invention, and the layer of a base material in order from the surface.
- Reference example 1 Preparation of reaction condensate of tetraethoxysilane and water: After adding 1.7 g of palladium chloride previously dissolved in 1.7 g of hydrochloric acid to 336 g of water, the mixture was stirred and dissolved. To this was added 564 g of tetraethoxysilane, and the mixture was stirred for 2 hours while heating to 50 ° C. with a mantle heater, and subjected to a condensation reaction to obtain a reaction product. The alcohol produced during this reaction was not fractionated. Before this reaction, water and tetraethoxysilane were not mixed and separated into two layers, but after the condensation reaction, they became a single layer. Therefore, it was found that the reaction rate of this reaction was 100%.
- This reaction product was a reaction condensate of tetraethoxysilane and water. Further, since the reaction product showed precipitation of palladium within 24 hours, it was found that palladium was not taken into this structure. In addition, the reaction solidified within 2 months at room temperature.
- Example 1 Preparation of palladium-containing silicon oligomer: After adding 1.7 g of palladium chloride previously dissolved in 1.7 g of hydrochloric acid to 336 g of ethylene glycol, the mixture was stirred and dissolved. To this was added 564 g of tetraethoxysilane, and the mixture was stirred for 2 hours while heating to 50 ° C. with a mantle heater, and subjected to a condensation reaction to obtain a reaction product. The alcohol produced during this reaction was not fractionated. In addition, before this reaction, ethylene glycol and tetraethoxysilane were not mixed but separated into two layers, but after a 2-hour condensation reaction, a single layer was formed. Therefore, it was found that the reaction rate of this reaction was 100%.
- Example 2 Preparation of palladium-containing silicon oligomer: After adding 1.7 g of palladium chloride previously dissolved in 1.7 g of hydrochloric acid to 380 g of 1,3-propylene glycol, the mixture was stirred and dissolved. To this, 521 g of tetraethoxysilane was added, stirred while heating to 50 ° C. with a mantle heater, and subjected to a condensation reaction for 2 hours to obtain a reaction product. The alcohol produced during this reaction was not fractionated. Before this reaction, 1,3-propylene glycol and tetraethoxysilane were not mixed and separated into two layers, but after a 2-hour condensation reaction, a single layer was formed. Therefore, it was found that the reaction rate of this reaction was 100%.
- Example 3 Preparation of palladium-containing silicon oligomer: After adding 1.7 g of palladium chloride previously dissolved in 1.7 g of hydrochloric acid to 248 g of ethylene glycol, the mixture was stirred and dissolved. To this, 641 g of tetrabutoxysilane was added, stirred while heating to 50 ° C. with a mantle heater, and subjected to a condensation reaction for 2 hours to obtain a reaction product. The alcohol produced during this reaction was not fractionated. Before this reaction, ethylene glycol and tetrabutoxysilane were not mixed and separated into two layers, but after a 2-hour condensation reaction, a single layer was formed. Therefore, it was found that the reaction rate of this reaction was 100%.
- Example 4 Preparation of palladium-containing silicon oligomer: After adding 1.7 g of palladium chloride previously dissolved in 1.7 g of hydrochloric acid to 405 g of ethylene glycol, the mixture was stirred and dissolved. To this, 496 g of tetramethoxysilane was added, stirred at room temperature (25 ° C.), and subjected to a condensation reaction for 2 hours to obtain a reaction product. The alcohol produced during this reaction was not fractionated. Before this reaction, ethylene glycol and tetramethoxysilane were not mixed and separated into two layers, but after a 2-hour condensation reaction, a single layer was formed. Therefore, it was found that the reaction rate of this reaction was 100%.
- Example 5 Preparation of iron-containing silicon oligomer: 6.7 g of iron chloride tetrahydrate was added to 335 g of ethylene glycol, and then stirred and dissolved. To this, 575 g of tetraethoxysilane was added, stirred while heating to 70 ° C. with a mantle heater, and subjected to a condensation reaction for 2 hours to obtain a reaction product. The alcohol produced during this reaction was not fractionated. Before this reaction, ethylene glycol and tetraethoxysilane were not mixed and separated into two layers, but after a 2-hour condensation reaction, a single layer was formed. Therefore, it was found that the reaction rate of this reaction was 100%.
- Example 6 Preparation of copper-containing silicon oligomer: After adding 5.5 g of copper chloride dihydrate to 336 g of ethylene glycol, the mixture was stirred and dissolved. To this, 563 g of tetraethoxysilane was added, stirred while heating to 90 ° C. with a mantle heater, and subjected to a condensation reaction for 2 hours to obtain a reaction product. The alcohol produced during this reaction was not fractionated. Before this reaction, ethylene glycol and tetraethoxysilane were not mixed and separated into two layers, but after a 2-hour condensation reaction, a single layer was formed. Therefore, it was found that the reaction rate of this reaction was 100%.
- Example 2 1 HNMR and 29 SiNMR measurements were performed in the same manner as in Example 1 to confirm that the condensation reaction between the ethoxy group of tetraethoxysilane and ethylene glycol occurred, and that the number of Si in the molecule was 2 to 4. confirmed.
- the silicon oligomer obtained above did not precipitate nickel even after 1 year. From this, it was considered that nickel was incorporated into the structure of the silicon oligomer. (Hereinafter, this is referred to as “Ni-containing silicon oligomer”).
- Example 8 Preparation of cobalt-containing silicon oligomers: After adding 8.1 g of cobalt chloride hexahydrate to 336 g of ethylene glycol, the mixture was stirred and dissolved. To this, 564 g of tetraethoxysilane was added, stirred while heating to 50 ° C. with a mantle heater, and subjected to a condensation reaction for 2 hours to obtain a reaction product. The alcohol produced during this reaction was not fractionated. Before this reaction, ethylene glycol and tetraethoxysilane were not mixed and separated into two layers, but after a 2-hour condensation reaction, a single layer was formed. Therefore, it was found that the reaction rate of this reaction was 100%.
- Coating agents 1 to 8 were obtained by adding and mixing the catalyst-containing metal silicon oligomers obtained in Examples 1 to 8 at a concentration of 150 ppm to the ethyl cell solob.
- Example 10 Plating on glass plate: Of the coating agents obtained in Example 9, the coating agents 1 to 5 and 7 to 8 were plated on glass plates as follows. First, a glass plate (2 ⁇ 5 cm) was immersed in the coating agent, and then pre-dried with warm air. Next, this was dried in an oven at 200 ° C. for 20 minutes and cooled to room temperature. Thereafter, this glass plate was immersed in an electroless nickel plating bath (manufactured by JCU: Enirex NI-100) at 40 ° C. for 7 minutes for plating.
- an electroless nickel plating bath manufactured by JCU: Enirex NI-100
- Example 9 the coating agent 6 obtained in Example 9 was plated using the same method as above except that the electroless nickel plating bath was changed to an electroless copper plating bath (manufactured by JCU: Evashield EC). Went. Finally, whether or not plating was deposited on the glass plate and the deposition area were evaluated according to the following evaluation criteria. The results are shown in Table 1.
- the wet area ((area coated after drying / area immersed in coating agent) ⁇ 100 (%)) after dipping the glass plate in the coating agent and drying in an oven was 80%.
- the coating agents 1 to 4 containing the Pd-containing oligomer were deposited at 100% of the wet area.
- Example 11 Plating on ABS plate Among the coating agents obtained in Example 9, the coating agents 1 to 5 and 7 to 8 were used to plate the ABS plate as follows. First, an ABS plate (2 ⁇ 5 cm) was immersed in the coating agent, and then pre-dried with warm air. Next, it was dried in an oven at 70 ° C. for 20 minutes and cooled to room temperature. Thereafter, the ABS plate was immersed in a dimethylamine borane aqueous solution (100 ppm) to reduce the metal of the catalyst-containing metal silicon oligomer contained in the coating agent. Further, this was washed with water and then immersed in an electroless nickel plating bath (manufactured by JCU: Enirex NI-100) at 40 ° C.
- an electroless nickel plating bath manufactured by JCU: Enirex NI-100
- Example 9 the coating agent 6 obtained in Example 9 was plated using the same method as above except that the electroless nickel plating bath was changed to an electroless copper plating bath (manufactured by JCU: Evashield EC). Went. Finally, whether or not plating was deposited on the ABS plate and the deposition area were evaluated based on the same evaluation criteria as in Example 10. The results are shown in Table 2.
- Plating was deposited on the ABS plate treated with all coating agents.
- the wet area after the ABS plate was dipped in the coating agent and dried in an oven was 80%.
- the coating agents 1 to 4 containing the Pd-containing oligomer had plating deposited at 100% of the wet area.
- Example 12 Preparation of coating agent with resin: 8.75 g of an acrylic resin (manufactured by Aika Kogyo Co., Ltd .: APX-1256) was added to 78.75 g of ethyl celsolob, and the mixture was stirred and dissolved. To this, the Pd-containing silicon oligomer 1 obtained in Example 1 was added and mixed in such a concentration that the palladium concentration became 150 ppm to obtain a coating agent 1 containing a resin.
- an acrylic resin manufactured by Aika Kogyo Co., Ltd .: APX-1256
- Example 13 Preparation of coating agent with resin: After adding and mixing the Pd-containing silicon oligomer 1 obtained in Example 1 in ethyl cersolob at a concentration of 150 ppm of palladium, further polyethylene powder (CERAFLOUR 990, manufactured by Big Kay Japan) has a solid content of 3%. It added and mixed by the density
- CERAFLOUR 990 manufactured by Big Kay Japan
- a glass plate (2 ⁇ 5 cm) was immersed in this resin-containing coating agent 2 and then pre-dried with warm air. Next, when this was dried in an oven at 200 ° C. for 20 minutes and cooled to room temperature, the wetted area was 100%.
- Example 14 Preparation of binary coating agent: 8.75 g of an acrylic resin (manufactured by Aika Kogyo Co., Ltd .: APX-1256) was added to 78.75 g of ethyl celsolob, and the mixture was stirred and dissolved.
- the binary coating agent 1 was obtained by adding and mixing the Pd-containing silicon oligomer 1 obtained in Example 1 and the Fe-containing silicon oligomer obtained in Example 5 at a concentration of 150 ppm each. It was. Further, the Fe-containing silicon oligomer obtained in Example 5 was replaced with the Cu-containing silicon oligomer obtained in Example 6, the Ni-containing silicon oligomer obtained in Example 7, and the Co-containing silicon oligomer obtained in Example 8.
- Binary coating agents 2 to 4 were obtained in the same manner as described above except that:
- Example 15 Plating on glass plate: Of the binary coating agents 1 to 4 obtained in Example 14, the coating agents 1 and 3 to 4 were plated on glass plates as follows. First, a glass plate (2 ⁇ 5 cm) was immersed in the coating agent, and then pre-dried with warm air. Next, this was dried in an oven at 200 ° C. for 20 minutes and cooled to room temperature. Thereafter, this glass plate was immersed in an electroless nickel plating bath (manufactured by JCU: Enilex NI-100) at 25 ° C. for 7 minutes for plating.
- an electroless nickel plating bath manufactured by JCU: Enilex NI-100
- the binary coating agent 3 obtained in Example 14 was used in the same manner as above except that the electroless nickel plating bath was changed to an electroless copper plating bath (manufactured by JCU: PB-506). Then, plating was performed. Further, the binary coating agent was changed to the coating agent containing the palladium-containing oligomer 1 obtained in Example 1, and the plating was performed in the same manner as described above was used as a control. In addition, since the temperature of the electroless plating bath is lower by 15 ° C. than the plating condition of Example 1, this control condition is a condition in which the plating is deposited only about several percent of the wet area. Finally, the increase ratio was calculated from the wetted area where plating was deposited on the control glass plate, the wetted area and the wetted area where plating was deposited on the glass plate obtained using the binary coating agent. The results are shown in Table 3.
- Example 16 Preparation of palladium-containing iron silicon oligomer: In Example 1, the reaction was performed in the same manner as in Example 1 except that 6.7 g of iron chloride tetrahydrate was added to 1.7 g of palladium chloride.
- the silicon oligomer obtained by this reaction was considered to have palladium and iron incorporated into its structure.
- Example 17 Preparation of coating agent: The palladium-containing / iron-silicon oligomer obtained in Example 16 was added to and mixed with ethyl cersolob at a concentration such that the total metal concentration of palladium and iron was 150 ppm to obtain a coating agent.
- Example 18 Plating on glass plate: When the coating agent obtained in Example 17 was used to plate a glass plate in the same manner as in the control of Example 15, the deposition area increased compared to the catalyst-containing metal silicon oligomer containing one type of catalyst metal. To do.
- the catalyst-containing metal silicon oligomer of the present invention can impart autocatalytic properties and conductivity regardless of the type of substrate.
- the catalyst-containing metal silicon oligomer of the present invention can be used for plating a substrate. more than
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemically Coating (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
- Catalysts (AREA)
Abstract
Description
少なくともn,n+1位またはn,n+2位(ただしnは1以上の整数)にヒドロキシ基が結合した多価アルコールとを、
触媒金属の存在下、
縮合反応させることにより得られる含触媒金属シリコンオリゴマーである。
少なくともn,n+1位またはn,n+2位(ただしnは1以上の整数)にヒドロキシ基が結合した多価アルコールとを、
触媒金属の存在下、
縮合反応させることを特徴とする含触媒金属シリコンオリゴマーの製造方法である。
テトラアルコキシシランと、
少なくともn,n+1位またはn,n+2位(ただしnは1以上の整数)にヒドロキシ基が結合した多価アルコールとを、
触媒金属の存在下、
縮合反応させることにより得られるものである。
テトラエトキシシランと水との反応縮合物の調製:
予め1.7gの塩酸に溶解させた塩化パラジウム1.7gを、水336gに添加した後、撹拌し、溶解させた。これにテトラエトキシシラン564gを添加し、マントルヒーターで50℃に加温しながら2時間撹拌し、縮合反応させて反応物を得た。なお、この反応の際に生成するアルコールは分留しなかった。また、この反応の前は、水とテトラエトキシシランは混和せずに、2層に分離していたが、縮合反応後は、単一層となった。そのため、この反応の反応率は100%であることがわかった。
含パラジウムシリコンオリゴマーの調製:
予め1.7gの塩酸に溶解させた塩化パラジウム1.7gを、エチレングリコール336gに添加した後、撹拌し、溶解させた。これにテトラエトキシシラン564gを添加し、マントルヒーターで50℃に加温しながら2時間撹拌し、縮合反応させて反応物を得た。なお、この反応の際に生成するアルコールは分留しなかった。また、この反応の前は、エチレングリコールとテトラエトキシシランは混和せずに、2層に分離していたが、2時間縮合反応後は、単一層となった。そのため、この反応の反応率は100%であることがわかった。
含パラジウムシリコンオリゴマーの調製:
予め1.7gの塩酸に溶解させた塩化パラジウム1.7gを、1,3-プロピレングリコール380gに添加した後、撹拌し、溶解させた。これにテトラエトキシシラン521gを添加し、マントルヒーターで50℃に加温しながら撹拌し、2時間縮合反応させて反応物を得た。なお、この反応の際に生成するアルコールは分留しなかった。この反応の前は、1,3-プロピレングリコールとテトラエトキシシランは混和せずに、2層に分離していたが、2時間縮合反応後は、単一層となった。そのため、この反応の反応率は100%であることがわかった。
含パラジウムシリコンオリゴマーの調製:
予め1.7gの塩酸に溶解させた塩化パラジウム1.7gを、エチレングリコール248gに添加した後、撹拌し、溶解させた。これにテトラブトキシシラン641gを添加し、マントルヒーターで50℃に加温しながら撹拌し、2時間縮合反応させて反応物を得た。なお、この反応の際に生成するアルコールは分留しなかった。この反応の前は、エチレングリコールとテトラブトキシシランは混和せずに、2層に分離していたが、2時間縮合反応後は、単一層となった。そのため、この反応の反応率は100%であることがわかった。
含パラジウムシリコンオリゴマーの調製:
予め1.7gの塩酸に溶解させた塩化パラジウム1.7gを、エチレングリコール405gに添加した後、撹拌し、溶解させた。これにテトラメトキシシラン496gを添加し、室温(25℃)で撹拌し、2時間縮合反応させて反応物を得た。なお、この反応の際に生成するアルコールは分留しなかった。この反応の前は、エチレングリコールとテトラメトキシシランは混和せずに、2層に分離していたが、2時間縮合反応後は、単一層となった。そのため、この反応の反応率は100%であることがわかった。
含鉄シリコンオリゴマーの調製:
塩化鉄四水和物6.7gを、エチレングリコール335gに添加した後、撹拌し、溶解させた。これにテトラエトキシシラン575gを添加し、マントルヒーターで70℃に加温しながら撹拌し、2時間縮合反応させて反応物を得た。なお、この反応の際に生成するアルコールは分留しなかった。この反応の前は、エチレングリコールとテトラエトキシシランは混和せずに、2層に分離していたが、2時間縮合反応後は、単一層となった。そのため、この反応の反応率は100%であることがわかった。
含銅シリコンオリゴマーの調製:
塩化銅二水和物5.5gを、エチレングリコール336gに添加した後、撹拌し、溶解させた。これにテトラエトキシシラン563gを添加し、マントルヒーターで90℃に加温しながら撹拌し、2時間縮合反応させて反応物を得た。なお、この反応の際に生成するアルコールは分留しなかった。この反応の前は、エチレングリコールとテトラエトキシシランは混和せずに、2層に分離していたが、2時間縮合反応後は、単一層となった。そのため、この反応の反応率は100%であることがわかった。
含ニッケルシリコンオリゴマーの調製:
塩化ニッケル六水和物8.4gを、エチレングリコール336gに添加した後、撹拌し、溶解させた。これにテトラエトキシシラン564gを添加し、マントルヒーターで100℃に加温しながら撹拌し、2時間縮合反応させて反応物を得た。なお、この反応の際に生成するアルコールは分留しなかった。この反応の前は、エチレングリコールとテトラエトキシシランは混和せずに、2層に分離していたが、2時間縮合反応後は、単一層となった。そのため、この反応の反応率は100%であることがわかった。
含コバルトシリコンオリゴマーの調製:
塩化コバルト六水和物8.1gを、エチレングリコール336gに添加した後、撹拌し、溶解させた。これにテトラエトキシシラン564gを添加し、マントルヒーターで50℃に加温しながら撹拌し、2時間縮合反応させて反応物を得た。なお、この反応の際に生成するアルコールは分留しなかった。この反応の前は、エチレングリコールとテトラエトキシシランは混和せずに、2層に分離していたが、2時間縮合反応後は、単一層となった。そのため、この反応の反応率は100%であることがわかった。
コーティング剤の調製:
エチルセルソロブに、実施例1~8で得られた含触媒金属シリコンオリゴマーを金属濃度が150ppmとなる濃度でそれぞれ添加、混合してコーティング剤1~8を得た。
ガラス板へのめっき:
実施例9で得られたコーティング剤のうち、コーティング剤1~5、7~8については、次のようにこれを利用してガラス板へめっきを行った。まず、コーティング剤中に、ガラス板(2×5cm)を浸漬した後、温風でプレ乾燥した。次に、これを200℃のオーブンにて20分間乾燥させ、室温まで冷却した。その後、このガラス板を40℃の無電解ニッケルめっき浴(JCU社製:エニレックスNI-100)に7分間浸漬し、めっきを行った。また、実施例9で得られたコーティング剤6については、無電解ニッケルめっき浴を無電解銅めっき浴(JCU社製:エバシールドEC)に変更する以外は上記と同様にこれを利用してめっきを行った。最後にガラス板にめっきが析出したかどうかと、析出面積を以下の評価基準で評価した。その結果を表1に示した。
(評価) (内容)
○ : 析出が100%以下50%以上
△ : 析出が50%未満
× : 析出無し
ABS板へのめっき:
実施例9で得られたコーティング剤のうち、コーティング剤1~5、7~8については、次のようにこれを利用してABS板へめっきを行った。まず、コーティング剤中に、ABS板(2×5cm)を浸漬した後、温風でプレ乾燥した。次に、これを70℃のオーブンにて20分間乾燥させ、室温まで冷却した。その後、このABS板をジメチルアミンボラン水溶液(100ppm)に浸漬し、コーティング剤に含まれる含触媒金属シリコンオリゴマーの金属の還元を行った。更に、これを水洗した後、40℃の無電解ニッケルめっき浴(JCU社製:エニレックスNI-100)に7分間浸漬し、めっきを行った。また、実施例9で得られたコーティング剤6については、無電解ニッケルめっき浴を無電解銅めっき浴(JCU社製:エバシールドEC)に変更する以外は上記と同様にこれを利用してめっきを行った。最後にABS板にめっきが析出したかどうかと、析出面積を実施例10と同様の評価基準で評価した。その結果を表2に示した。
樹脂入りコーティング剤の調製:
アクリル樹脂(アイカ工業株式会社製:APX-1256)8.75gを、エチルセルソロブ78.75gに添加し、撹拌し溶解させた。これに実施例1で得られた含Pdシリコンオリゴマー1をパラジウム濃度が150ppmとなる濃度で添加、混合して樹脂入りコーティング剤1を得た。
樹脂入りコーティング剤の調製:
エチルセルソロブに実施例1で得られた含Pdシリコンオリゴマー1をパラジウム濃度が150ppmとなる濃度で添加、混合した後、更にポリエチレン粉末(ビックケーミージャパン社製:CERAFLOUR990)を固形分が3%となる濃度で添加、混合し、樹脂入りコーティング剤2を得た。
2元系コーティング剤の調製:
アクリル樹脂(アイカ工業株式会社製:APX-1256)8.75gを、エチルセルソロブ78.75gに添加し、撹拌し溶解させた。これに実施例1で得られた含Pdシリコンオリゴマー1および実施例5で得られた含Feシリコンオリゴマーを、金属濃度がそれぞれ150ppmとなる濃度で添加、混合して2元系コーティング剤1を得た。また、実施例5で得られた含Feシリコンオリゴマーを、実施例6で得られた含Cuシリコンオリゴマー、実施例7で得られた含Niシリコンオリゴマー、実施例8で得られた含Coシリコンオリゴマーに変更する以外は、上記と同様にして2元系コーティング剤2~4を得た。
ガラス板へのめっき:
実施例14で得られた2元系コーティング剤1~4のうち、コーティング剤1、3~4については、次のようにこれを利用してガラス板へめっきを行った。まず、コーティング剤中に、ガラス板(2×5cm)を浸漬した後、温風でプレ乾燥した。次に、これを200℃のオーブンにて20分間乾燥させ、室温まで冷却した。その後、このガラス板を25℃の無電解ニッケルめっき浴(JCU社製:エニレックスNI-100)に7分間浸漬し、めっきを行った。また、実施例14で得られた2元系コーティング剤3については、無電解ニッケルめっき浴を無電解銅めっき浴(JCU社製:PB-506)に変更する以外は上記と同様にこれを利用してめっきを行った。また、それぞれ2元系コーティング剤を実施例1で得られた含パラジウムオリゴマー1を含むコーティング剤に変更したもので、上記と同様にしてめっきを行ったものを対照とした。なお、この対照の条件は、実施例1のめっき条件よりも無電解めっき浴の温度を15℃下げているため、めっきは濡れ面積の数%程度しか析出しない条件である。最後に対照のガラス板にめっきが析出した濡れ面積と、その濡れ面積と2元系コーティング剤を用いて得られたガラス板にめっきが析出した濡れ面積から増加倍率を算出した。その結果を表3に示した。
含パラジウム・鉄シリコンオリゴマーの調製:
実施例1において、塩化パラジウム1.7gに追加して塩化鉄四水和物6.7gを添加する以外は、実施例1と同様にして反応を行った。
コーティング剤の調製:
エチルセルソロブに、実施例16で得られた含パラジウム・鉄シリコンオリゴマーをパラジウムと鉄の総金属濃度が150ppmとなる濃度で添加、混合してコーティング剤を得た。
ガラス板へのめっき:
実施例17で得られたコーティング剤を利用して、実施例15の対照と同様にしてガラス板へめっきを行うと、1種類の触媒金属を含有する含触媒金属シリコンオリゴマーよりも析出面積が増加する。
以 上
Claims (20)
- テトラアルコキシシランと、
少なくともn,n+1位またはn,n+2位(ただしnは1以上の整数)にヒドロキシ基が結合した多価アルコールとを、
触媒金属の存在下、
縮合反応させることにより得られる含触媒金属シリコンオリゴマー。 - 縮合反応の際に生成するアルコールを分留しないものである請求項1記載の含触媒金属シリコンオリゴマー。
- テトラアルコキシシランが、テトラメトキシシラン、テトラエトキシシランおよびテトラブトキシシランからなる群から選ばれる1種または2種以上である請求項1記載の含触媒金属シリコンオリゴマー。
- 少なくともn,n+1位またはn,n+2位(ただしnは1以上の整数)にヒドロキシ基が結合した多価アルコールが、エチレングリコールおよび/または1,3-プロピレングリコールである請求項1記載の含触媒金属シリコンオリゴマー。
- 触媒金属が、鉄、ニッケル、コバルト、銅およびパラジウムからなる群から選ばれる1種または2種以上である請求項1記載の含触媒金属シリコンオリゴマー。
- テトラアルコキシシランと、
少なくともn,n+1位またはn,n+2位(ただしnは1以上の整数)にヒドロキシ基が結合した多価アルコールとを、
触媒金属の存在下、
縮合反応させることを特徴とする含触媒金属シリコンオリゴマーの製造方法。 - 縮合反応の際に生成するアルコールを分留しないものである請求項6記載の含触媒金属シリコンオリゴマーの製造方法。
- テトラアルコキシシランが、テトラメトキシシラン、テトラエトキシシランおよびテトラブトキシシランからなる群から選ばれる1種または2種以上である請求項6記載の含触媒金属シリコンオリゴマーの製造方法。
- 少なくともn,n+1位またはn,n+2位(ただしnは1以上の整数)にヒドロキシ基が結合した多価アルコールが、エチレングリコールおよび/または1,3-プロピレングリコールである請求項6記載の含触媒金属シリコンオリゴマーの製造方法。
- 触媒金属が、鉄、ニッケル、コバルト、銅およびパラジウムからなる群から選ばれる1種または2種以上である請求項6記載の含触媒金属シリコンオリゴマーの製造方法。
- 請求項1~5の何れかに記載の含触媒金属シリコンオリゴマーを含有することを特徴とするコーティング剤。
- 更に、アクリル系樹脂、ウレタン系樹脂、フェノール系樹脂およびエポキシ系樹脂からなる群から選ばれる樹脂の1種または2種以上を含有するものである請求項11記載のコーティング剤。
- 自己触媒性付与用である請求項11または12記載のコーティング剤。
- 導電性付与用である請求項11または12記載のコーティング剤。
- 基材を、請求項11~14の何れかに記載のコーティング剤で処理した後、触媒金属の活性化処理を行い、次いで、めっきを行うことを特徴とする基材へのめっき方法。
- 触媒金属の活性化処理が、100℃以上で行う加熱処理である請求項15記載の基材へのめっき方法。
- 触媒金属の活性化処理が、100℃未満で行う加熱処理の後、化学還元処理を行うものである請求項15記載の基材へのめっき方法。
- 化学還元処理が、次亜リン酸、ジメチルアミンボラン、ホルマリン、水素化ホウ素ナトリウム、ヒドラジンからなる群から選ばれる1種または2種以上を用いて行うものである請求項17記載の基材へのめっき方法。
- 基材が、難めっき性基材である請求項15記載の基材へのめっき方法。
- 請求項15~19の何れかに記載の基材へのめっき方法により得られる、表面から順に、めっきした金属の層、含触媒金属シリコンオリゴマーを含むコーティング剤の層、基材の層からなるめっき製品。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016538459A JP6709155B2 (ja) | 2014-08-01 | 2015-07-31 | 含触媒金属シリコンオリゴマー、その製造方法および含触媒金属シリコンオリゴマーの用途 |
CN201580034265.6A CN106471001B (zh) | 2014-08-01 | 2015-07-31 | 含催化剂金属的有机硅低聚物、其制造方法以及含催化剂金属的有机硅低聚物的用途 |
KR1020167036056A KR102445276B1 (ko) | 2014-08-01 | 2015-07-31 | 촉매 함유 금속 실리콘 올리고머, 그의 제조방법 및 촉매 함유 금속 실리콘 올리고머의 용도 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-157517 | 2014-08-01 | ||
JP2014157517 | 2014-08-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016017792A1 true WO2016017792A1 (ja) | 2016-02-04 |
Family
ID=55217687
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/071752 WO2016017792A1 (ja) | 2014-08-01 | 2015-07-31 | 含触媒金属シリコンオリゴマー、その製造方法および含触媒金属シリコンオリゴマーの用途 |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP6709155B2 (ja) |
KR (1) | KR102445276B1 (ja) |
CN (1) | CN106471001B (ja) |
TW (1) | TWI684616B (ja) |
WO (1) | WO2016017792A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11236251B2 (en) | 2017-05-31 | 2022-02-01 | Kolon Industries, Inc. | Resin composition for coating, and coating film comprising cured product thereof as coating layer |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018221980A1 (ko) * | 2017-05-31 | 2018-12-06 | 코오롱인더스트리 주식회사 | 코팅용 수지 조성물 및 이의 경화물을 코팅층으로 포함하는 코팅필름 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN85103438A (zh) * | 1985-04-02 | 1986-10-15 | 山东大学 | 新型室温硫化硅橡胶的制作法 |
JP2004231560A (ja) * | 2003-01-30 | 2004-08-19 | Nippon Shokubai Co Ltd | アルコキシシランの製造方法 |
JP2007070353A (ja) * | 2005-08-12 | 2007-03-22 | Shiseido Co Ltd | 水溶性シラン誘導体の製造方法 |
JP2008531787A (ja) * | 2005-02-23 | 2008-08-14 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | ケイ素含有ポリトリメチレンホモ−またはコポリエーテル組成物 |
WO2014207885A1 (ja) * | 2013-06-28 | 2014-12-31 | 株式会社Jcu | シリコンオリゴマーおよびその製造方法 |
WO2014207886A1 (ja) * | 2013-06-28 | 2014-12-31 | 株式会社Jcu | シリコンオリゴマーを含有するコーティング剤およびその用途 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NO138030C (no) * | 1970-09-24 | 1978-06-14 | Mobil Oil Corp | Lagringsbestandig, sinkstoevholdig maling, omfattende et bindemiddel paa basis av organiske silikater |
JPH10251516A (ja) * | 1997-03-14 | 1998-09-22 | Chisso Corp | シランオリゴマー組成物 |
JP2000212510A (ja) * | 1999-01-22 | 2000-08-02 | Matsushita Electric Works Ltd | 機能性無機塗料、その塗装方法および機能性塗装品 |
KR100495164B1 (ko) * | 2000-04-25 | 2005-06-14 | 가부시키 가이샤 닛코 마테리알즈 | 도금 전처리제 및 그것을 사용한 금속도금 방법 |
KR101001441B1 (ko) * | 2004-08-17 | 2010-12-14 | 삼성전자주식회사 | 유무기 금속 하이브리드 물질 및 이를 포함하는 유기절연체 조성물 |
CN101243094A (zh) * | 2005-08-12 | 2008-08-13 | 株式会社资生堂 | 水溶性金属醇化物衍生物、其制备方法及含有该物质的固体凝胶状外用剂 |
JP2011162806A (ja) | 2010-02-04 | 2011-08-25 | Rohm & Haas Denshi Zairyo Kk | 無電解めっきを行うための前処理液 |
-
2015
- 2015-07-31 KR KR1020167036056A patent/KR102445276B1/ko active IP Right Grant
- 2015-07-31 JP JP2016538459A patent/JP6709155B2/ja active Active
- 2015-07-31 TW TW104124915A patent/TWI684616B/zh active
- 2015-07-31 WO PCT/JP2015/071752 patent/WO2016017792A1/ja active Application Filing
- 2015-07-31 CN CN201580034265.6A patent/CN106471001B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN85103438A (zh) * | 1985-04-02 | 1986-10-15 | 山东大学 | 新型室温硫化硅橡胶的制作法 |
JP2004231560A (ja) * | 2003-01-30 | 2004-08-19 | Nippon Shokubai Co Ltd | アルコキシシランの製造方法 |
JP2008531787A (ja) * | 2005-02-23 | 2008-08-14 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | ケイ素含有ポリトリメチレンホモ−またはコポリエーテル組成物 |
JP2007070353A (ja) * | 2005-08-12 | 2007-03-22 | Shiseido Co Ltd | 水溶性シラン誘導体の製造方法 |
WO2014207885A1 (ja) * | 2013-06-28 | 2014-12-31 | 株式会社Jcu | シリコンオリゴマーおよびその製造方法 |
WO2014207886A1 (ja) * | 2013-06-28 | 2014-12-31 | 株式会社Jcu | シリコンオリゴマーを含有するコーティング剤およびその用途 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11236251B2 (en) | 2017-05-31 | 2022-02-01 | Kolon Industries, Inc. | Resin composition for coating, and coating film comprising cured product thereof as coating layer |
CN115851117A (zh) * | 2017-05-31 | 2023-03-28 | 可隆工业株式会社 | 用于涂覆的树脂组合物及含其固化产物作为涂层的涂覆膜 |
Also Published As
Publication number | Publication date |
---|---|
TW201619242A (zh) | 2016-06-01 |
CN106471001B (zh) | 2019-05-07 |
JPWO2016017792A1 (ja) | 2017-07-13 |
KR102445276B1 (ko) | 2022-09-20 |
TWI684616B (zh) | 2020-02-11 |
CN106471001A (zh) | 2017-03-01 |
KR20170040125A (ko) | 2017-04-12 |
JP6709155B2 (ja) | 2020-06-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI524939B (zh) | 用於無電金屬化之安定催化劑 | |
JP6124955B2 (ja) | 無電解銅めっき組成物 | |
US9353443B2 (en) | Stable catalysts for electroless metallization | |
EP1876261B1 (en) | Electroless copper and redox couples | |
JP6047707B2 (ja) | 前処理液を用いた無電解銅メッキ方法 | |
JP6047713B2 (ja) | 無電解銅メッキ方法 | |
TWI499691B (zh) | 用於無電金屬化之安定無錫催化劑 | |
TWI567233B (zh) | 以含有嘧啶衍生物之鹼性安定性催化劑無電金屬化介電質 | |
JP6322691B2 (ja) | プリント回路基板及びスルーホールの無電解金属化のための環境に優しい安定触媒 | |
TW200809004A (en) | Formaldehyde free electroless copper compositions | |
JP2012052222A (ja) | ナノ粒子の組成物 | |
JP6709155B2 (ja) | 含触媒金属シリコンオリゴマー、その製造方法および含触媒金属シリコンオリゴマーの用途 | |
JP6322692B2 (ja) | プリント回路基板及びスルーホールの無電解金属化のための環境に優しい安定触媒 | |
JP6322690B2 (ja) | プリント回路基板及びスルーホールの無電解金属化のための環境に優しい安定触媒 | |
Rahmani et al. | Impact of barium in improving corrosion resistance and properties of electroless Ni–Ba–B alloy deposits | |
KR102644596B1 (ko) | 기판 위에 회로의 형성방법 | |
JP2014214353A (ja) | 電磁波透過性材料 | |
JP6600506B2 (ja) | 基材の所望の部位への金属めっき方法およびこの方法により得られる金属めっき製品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15827693 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016538459 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20167036056 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15827693 Country of ref document: EP Kind code of ref document: A1 |