JP2018094787A - Rubber elastic body formed with silver mirror film layer and method for producing the same - Google Patents
Rubber elastic body formed with silver mirror film layer and method for producing the same Download PDFInfo
- Publication number
- JP2018094787A JP2018094787A JP2016240927A JP2016240927A JP2018094787A JP 2018094787 A JP2018094787 A JP 2018094787A JP 2016240927 A JP2016240927 A JP 2016240927A JP 2016240927 A JP2016240927 A JP 2016240927A JP 2018094787 A JP2018094787 A JP 2018094787A
- Authority
- JP
- Japan
- Prior art keywords
- silver mirror
- film layer
- mirror film
- elastic body
- rubber elastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 258
- 239000004332 silver Substances 0.000 title claims abstract description 256
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 255
- 229920001971 elastomer Polymers 0.000 title claims abstract description 118
- 239000005060 rubber Substances 0.000 title claims abstract description 118
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 101
- 239000011248 coating agent Substances 0.000 claims abstract description 98
- 239000000463 material Substances 0.000 claims abstract description 66
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 45
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 32
- 229920005862 polyol Polymers 0.000 claims abstract description 30
- 150000003077 polyols Chemical class 0.000 claims abstract description 25
- 239000010410 layer Substances 0.000 claims description 205
- 239000003973 paint Substances 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 59
- 239000002987 primer (paints) Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000008119 colloidal silica Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- 239000004672 reactive softener Substances 0.000 claims description 17
- 229920001610 polycaprolactone Polymers 0.000 claims description 12
- 239000004632 polycaprolactone Substances 0.000 claims description 12
- 239000004902 Softening Agent Substances 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000010408 film Substances 0.000 description 353
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 45
- 238000005452 bending Methods 0.000 description 40
- 239000000243 solution Substances 0.000 description 37
- 238000012360 testing method Methods 0.000 description 26
- 244000043261 Hevea brasiliensis Species 0.000 description 23
- 229920003052 natural elastomer Polymers 0.000 description 23
- 229920001194 natural rubber Polymers 0.000 description 23
- -1 amine compound Chemical class 0.000 description 18
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 238000005259 measurement Methods 0.000 description 16
- 238000005507 spraying Methods 0.000 description 14
- 239000002585 base Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 239000007921 spray Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 150000003378 silver Chemical class 0.000 description 9
- 229910001923 silver oxide Inorganic materials 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000007747 plating Methods 0.000 description 8
- 229920002635 polyurethane Polymers 0.000 description 8
- 239000004814 polyurethane Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 229920002943 EPDM rubber Polymers 0.000 description 7
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 7
- 229920005549 butyl rubber Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 229940100890 silver compound Drugs 0.000 description 7
- 150000003379 silver compounds Chemical class 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- HAAYBYDROVFKPU-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.N.[Ag+].[O-][N+]([O-])=O HAAYBYDROVFKPU-UHFFFAOYSA-N 0.000 description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 description 6
- 239000011254 layer-forming composition Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 239000002932 luster Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NKUFAKIEICOTFD-UHFFFAOYSA-N [Ag]=O.C(CCC)N Chemical compound [Ag]=O.C(CCC)N NKUFAKIEICOTFD-UHFFFAOYSA-N 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 230000003139 buffering effect Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- 230000004931 aggregating effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- JMPXSWBXXUOKFP-UHFFFAOYSA-N 2-ethylhexylazanium;n-(2-ethylhexyl)carbamate Chemical compound CCCCC(CC)C[NH3+].CCCCC(CC)CNC([O-])=O JMPXSWBXXUOKFP-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 1
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical class N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- IBAHLNWTOIHLKE-UHFFFAOYSA-N cyano cyanate Chemical compound N#COC#N IBAHLNWTOIHLKE-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LFLZOWIFJOBEPN-UHFFFAOYSA-N nitrate, nitrate Chemical compound O[N+]([O-])=O.O[N+]([O-])=O LFLZOWIFJOBEPN-UHFFFAOYSA-N 0.000 description 1
- OTCVAHKKMMUFAY-UHFFFAOYSA-N oxosilver Chemical class [Ag]=O OTCVAHKKMMUFAY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001521 polyalkylene glycol ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- AQHHHDLHHXJYJD-UHFFFAOYSA-N propranolol Chemical compound C1=CC=C2C(OCC(O)CNC(C)C)=CC=CC2=C1 AQHHHDLHHXJYJD-UHFFFAOYSA-N 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- VFWRGKJLLYDFBY-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag].[Ag] VFWRGKJLLYDFBY-UHFFFAOYSA-N 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Images
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、銀鏡膜層が形成されたゴム弾性体及びその製造方法に関し、特に塗装法によって容易に形成することができ、しかも外観や銀鏡膜層の付着性も良好な、銀鏡膜層が形成されたゴム弾性体及びその製造方法に関する。 The present invention relates to a rubber elastic body on which a silver mirror film layer is formed and a method for producing the rubber elastic body, and in particular, a silver mirror film layer that can be easily formed by a coating method and has good appearance and adhesion of the silver mirror film layer. The present invention relates to a rubber elastic body and a manufacturing method thereof.
銀（Ａｇ）は、光の反射率が可視領域において高く、美しい金属光沢を有している。樹脂や金属等の基材上に銀鏡膜層を形成すると美しい金属光沢を呈するので、自動車の内装部品や外装部品、携帯電話、ノートパソコン、化粧品容器等に銀鏡膜層を施すことが期待される。例えば、自動車は、自動車の主材料（ほとんどの場合は、鋼板やプラスチック板）の保護及び自動車の美観の向上を目的として、塗装が施されている。同一形状、同一性能の自動車を比べると、美しく塗装された車の方が良く見え、商品としての価値が向上する。メタリック塗装は、金属的な質感に高級感があり、車の外観を見た際に、車を見る角度によって色相が異なって見え、車の形状にメリハリを与えることができるので、車の塗装として人気がある。車のメタリック塗装は、光輝材としてアルミフレークが多く使用されている。このようなメタリック塗装は他の製品おいても採用されており、高級品では光輝材ないし鏡面形成膜として銀の使用が検討されている。 Silver (Ag) has a high reflectance in the visible region and a beautiful metallic luster. When a silver mirror film layer is formed on a substrate such as a resin or metal, it exhibits a beautiful metallic luster. Therefore, it is expected to apply a silver mirror film layer to automobile interior parts and exterior parts, mobile phones, laptop computers, cosmetic containers, etc. . For example, automobiles are painted for the purpose of protecting the main materials of automobiles (in most cases, steel plates and plastic plates) and improving the aesthetics of automobiles. Compared to cars with the same shape and performance, a beautifully painted car looks better and increases its value as a product. Metallic paint has a high-class metallic texture, and when you look at the exterior of the car, the color looks different depending on the angle at which you look at the car, and it can give a sharp shape to the shape of the car. popular. Aluminum flakes are often used as metallic luster for car metallic paint. Such metallic coating is also used in other products, and the use of silver as a bright material or a mirror surface forming film is being studied in high-grade products.
従来、基材に銀鏡膜を形成する方法として、アンモニア性硝酸銀溶液を用いた銀鏡反応による銀鏡メッキがよく知られている。このアンモニア性硝酸銀溶液を用いた銀鏡メッキは、銀鏡膜にメッキ特有の白亜化（白化又はシケともいう。）を生じたり、銀鏡膜にクラックが生じたり、銀鏡膜の膜厚が均一にならなかったり、銀ナノ粒子の凝集にばらつきがある等の原因により、銀鏡面の発色（金属光沢）にムラを生じたりすることがある。さらに、この銀鏡メッキは、本来銀鏡メッキを施す必要がない部分が銀鏡メッキされてしまったりすることもあり、不良率が高いという問題や、形成した銀鏡膜面が基材等の表面から剥がれやすいという問題もある。 Conventionally, silver mirror plating by silver mirror reaction using an ammoniacal silver nitrate solution is well known as a method for forming a silver mirror film on a substrate. Silver mirror plating using this ammoniacal silver nitrate solution may cause plating-induced chalking (also known as whitening or shining) in the silver mirror film, cracks in the silver mirror film, and the film thickness of the silver mirror film may not be uniform. In some cases, the color of the silver mirror surface (metallic luster) may become uneven due to variations in the aggregation of silver nanoparticles. Furthermore, this silver mirror plating may cause the part that does not need to be silver mirror plated to be silver mirror plated, which has a high defect rate, and the formed silver mirror film surface is easily peeled off from the surface of the substrate or the like. There is also a problem.
このようなアンモニア性硝酸銀溶液を用いた銀鏡メッキの問題点を解決するために、銀化合物錯体としてアンモニウムに換えてアミン化合物やアンモニウムカルバメート系化合物が配位した銀化合物錯体を用いることが知られている。例えば、特許文献１（特許第５６１０３５９号公報）には、アルコール系溶媒中に、銀化合物の銀原子にアンモニウムカルバメート系化合物が配位した第１の錯体と、銀化合物の銀原子にアミン系化合物が配位した第２の錯体と、還元剤と、を含み、前記第１の錯体と前記第２の錯体との混合割合は、銀原子のモル比で、６：４〜８：２である、銀鏡膜層形成組成液、銀鏡膜層形成組成液の製造方法及び銀鏡膜塗面の形成方法の発明が開示されている。 In order to solve the problem of silver mirror plating using such an ammoniacal silver nitrate solution, it is known to use a silver compound complex in which an amine compound or an ammonium carbamate compound is coordinated instead of ammonium as a silver compound complex. Yes. For example, Patent Document 1 (Japanese Patent No. 5610359) discloses a first complex in which an ammonium carbamate compound is coordinated to a silver atom of a silver compound in an alcohol solvent, and an amine compound to the silver atom of the silver compound. And a reducing agent, and the mixing ratio of the first complex and the second complex is 6: 4 to 8: 2 in terms of the molar ratio of silver atoms. The invention of a silver mirror film layer forming composition liquid, a method of producing a silver mirror film layer forming composition liquid, and a method of forming a silver mirror film coating surface is disclosed.
同じく特許文献２（特許第５２４３４０９号公報）には、下記化学式１の１つ以上の銀化合物と、下記化学式２ないし化学式４から選択される１種又は２種以上のアンモニウムカルバメート系又はアンモニウムカーボネート系化合物とを反応して得られる銀錯体化合物を含有することを特徴とする反射膜コーティング液組成物が開示されている。 Similarly, Patent Document 2 (Japanese Patent No. 5243409) discloses one or more silver compounds of the following chemical formula 1 and one or more ammonium carbamate or ammonium carbonate compounds selected from the following chemical formulas 2 to 4. A reflective film coating solution composition comprising a silver complex compound obtained by reacting with a compound is disclosed.
さらに、一旦銀ナノ粒子を形成してから塗膜として銀鏡膜層を形成する方法も知られている。例えば、特許文献３（特許第５９５０４２７号公報）には、アルコール溶媒中にスチレン−無水マレイン酸樹脂構造を有し、前記無水マレイン酸の一部が末端水酸基のポリアルキレングリコール又は末端アミノ基のポリアルキレングリコールで変性されているものからなる酸価が１５０以下の高分子分散剤を溶解させるとともに、酸化銀及び炭酸銀から選択される少なくとも１種の銀化合物を分散させたアルコール溶液を用い、前記アルコール溶液中に超音波を照射することにより、銀ナノ粒子が分散したアルコール溶液からなる銀鏡膜層形成用塗装液を作成し、この銀鏡膜層形成用組成液を被塗装物の表面にスプレー塗装して常温下で乾燥することにより、銀鏡膜層を形成する方法が示されている。 Furthermore, a method of once forming silver nanoparticles and then forming a silver mirror film layer as a coating film is also known. For example, in Patent Document 3 (Japanese Patent No. 5950427), a polystyrene glycol having a styrene-maleic anhydride resin structure in an alcohol solvent and a part of the maleic anhydride being a terminal hydroxyl group or a terminal amino group is disclosed. Using an alcohol solution in which at least one silver compound selected from silver oxide and silver carbonate is dispersed while dissolving a polymer dispersant having an acid value of 150 or less, which is modified with alkylene glycol, By irradiating the alcohol solution with ultrasonic waves, a coating solution for forming a silver mirror film layer consisting of an alcohol solution in which silver nanoparticles are dispersed is prepared, and this silver mirror film layer forming composition solution is spray-coated on the surface of the object to be coated. A method of forming a silver mirror film layer by drying at room temperature is shown.
ところで、これらの銀鏡膜層は、一般的には、基材として金属表面やプラスチック表面等、硬質な表面に対して形成されている。このような硬質な表面に対しては、上述した化学メッキ法だけでなく、蒸着法やスパッタリング法などによっても銀鏡膜層を形成することができる。しかし、ゴム弾性体の表面に銀鏡膜層を形成する方法は、銀鏡膜層の変形に対する追随性不備による亀裂の発生や密着性不良が生じる等に問題点が存在するため、実用化が進んでいない。 By the way, these silver mirror film layers are generally formed on a hard surface such as a metal surface or a plastic surface as a base material. A silver mirror film layer can be formed on such a hard surface not only by the chemical plating method described above but also by a vapor deposition method or a sputtering method. However, the method of forming a silver mirror film layer on the surface of a rubber elastic body has been put into practical use because there are problems such as the occurrence of cracks and poor adhesion due to inadequate followability to deformation of the silver mirror film layer. Not in.
なお、ゴム弾性体表面に対して銀鏡膜層を形成する方法自体は、既に公知である。例えば、特許文献４（特開平０６−３４３６９０号公報）には、ゴムに還元剤溶液を用いて表面洗浄処理を行った後、グリオキサールで処理し、次いでアンモニア性硝酸銀溶液で処理し、必要により更に金属の塩化物水溶液で処理することにより、ゴム表面を銀で被覆した抗菌性ゴムを製造する方法が示されている。 The method itself for forming the silver mirror film layer on the rubber elastic body surface is already known. For example, in Patent Document 4 (Japanese Patent Laid-Open No. 06-343690), a rubber is subjected to a surface cleaning treatment using a reducing agent solution, then treated with glyoxal, then treated with an ammoniacal silver nitrate solution, and further if necessary. A method for producing an antibacterial rubber having a rubber surface coated with silver by treatment with an aqueous metal chloride solution is shown.
また、特許文献５（特開２０１０−１１０７０１号公報）には、樹脂成分及び銀ナノコロイドのゼータ電位を中和させる凝集剤を含有させた軟質樹脂層と、この軟質樹脂層上に形成された樹脂成分及び銀ナノコロイドを含む印刷インクを用いて塗布または印刷された表面層とを有し、銀ナノコロイドを選択的に凝集せしめることによって、下地層表面に銀ナノコロイドを凝集・偏析させて、所望の銀金属光沢層を付与し、柔軟な部材に対しても剥離・欠落の問題を解決できる銀金属光沢薄膜の形成方法が示されている。 Further, in Patent Document 5 (Japanese Patent Laid-Open No. 2010-110701), a soft resin layer containing a resin component and an aggregating agent that neutralizes the zeta potential of the silver nanocolloid and a soft resin layer formed on the soft resin layer are formed. It has a surface layer coated or printed using a printing ink containing a resin component and silver nanocolloid, and the silver nanocolloid is aggregated and segregated on the surface of the underlayer by selectively aggregating the silver nanocolloid. In addition, a method for forming a silver metal glossy thin film that can provide a desired silver metal gloss layer and solve the problem of peeling and missing even for a flexible member is shown.
上記特許文献４に示されている抗菌性ゴムの製造方法は、アンモニア性硝酸銀溶液を用いた銀鏡メッキ法を採用しているため、上述した種々の問題点が存在しており、ゴム弾性体表面に銀鏡膜層を形成する方法としては直ちには採用し難いだけでなく、得られた銀鏡膜層の変形追従性に難点がある。また、上記特許文献５に示されている銀金属光沢薄膜の形成方法は、下地層に銀コロイドを凝集、吸着させる必要があるため、例えば、下地層及び表面層とも厚さ５０〜５００μｍ、好ましくは１００〜３００μｍと、極端な厚膜となっている。そのため、高価な銀コロイドが多量に必要であり、経済的に実用性に欠ける。また厚塗りの工程が煩雑で、表面層の上に凝集剤を含む液状層を積層させたり、表面層に電場印加を推奨しており、施工性に問題がある。加えて、上記特許文献５に示されている方法で得られた銀金属光沢薄膜も、変形追従性に難点が存在している。 The manufacturing method of the antibacterial rubber disclosed in Patent Document 4 employs a silver mirror plating method using an ammoniacal silver nitrate solution, and thus has the various problems described above. In addition, it is difficult to immediately adopt a method for forming a silver mirror film layer, and there is a problem in deformation followability of the obtained silver mirror film layer. In addition, the method for forming a silver metallic glossy thin film disclosed in Patent Document 5 requires that the silver colloid be aggregated and adsorbed on the underlayer. For example, both the underlayer and the surface layer have a thickness of 50 to 500 μm, preferably Is an extremely thick film of 100 to 300 μm. Therefore, a large amount of expensive silver colloid is required, which is economically impractical. Also, the thick coating process is complicated, and a liquid layer containing a flocculant is laminated on the surface layer, or application of an electric field to the surface layer is recommended, and there is a problem in workability. In addition, the silver metal glossy thin film obtained by the method disclosed in Patent Document 5 also has a problem in deformation followability.
一方、ゴム弾性体表面に銀鏡膜層を形成する方法として上記特許文献１〜３に示されているアミン化合物やアンモニウムカルバメート系化合物が配位した銀化合物錯体溶液から銀鏡膜層を形成する方法ないし一旦銀ナノ粒子を形成してから塗膜として銀鏡膜層を形成する方法を採用すると、アンモニア性硝酸銀溶液を用いた銀鏡メッキの場合よりも均一で、高反射率な銀鏡膜層が得られるという優れた効果を奏する。しかしながら、これらの方法を採用してゴム弾性体の表面に銀鏡膜層を形成しても、得られた銀鏡膜層の変形追従性が低いという課題がある。 On the other hand, as a method for forming a silver mirror film layer on the surface of a rubber elastic body, a method for forming a silver mirror film layer from a silver compound complex solution coordinated with an amine compound or an ammonium carbamate compound shown in Patent Documents 1 to 3 above. Once the silver nanoparticle is formed and then the silver mirror film layer is formed as a coating film, a silver mirror film layer that is more uniform and has a higher reflectivity than that obtained by silver mirror plating using an ammoniacal silver nitrate solution is obtained. Excellent effect. However, even if these methods are employed to form a silver mirror film layer on the surface of the rubber elastic body, there is a problem that the obtained silver mirror film layer has low deformation followability.
本発明は、上述した従来例のゴム弾性体の表面に銀鏡膜層を形成する際の問題点を解決すべくなされたものである。すなわち、本発明は、ゴム弾性体表面に形成する下塗り塗料及び銀鏡膜層の表面に形成する上塗り塗料の物性を見直し、さらには銀鏡膜層形成用組成物の組成をも見直すことにより、銀鏡膜層の変形追従性が良好で、外観や銀鏡膜層の付着性も良好な、銀鏡膜層が形成されたゴム弾性体及びその製造方法を提供することを目的とする。 The present invention has been made to solve the problems in forming a silver mirror film layer on the surface of the rubber elastic body of the conventional example described above. That is, the present invention provides a silver mirror film by reviewing the physical properties of the undercoat paint formed on the surface of the rubber elastic body and the top coat paint formed on the surface of the silver mirror film layer, and further reviewing the composition of the silver mirror film layer forming composition. An object is to provide a rubber elastic body on which a silver mirror film layer is formed and a method for producing the rubber elastic body, in which the deformation followability of the layer is good, the appearance and the adhesion of the silver mirror film layer are also good.
本発明の第１の態様の銀鏡膜層が形成されたゴム弾性体は、ゴム弾性体の表面に形成された下塗り塗膜、前記下塗り塗膜の表面に形成された銀鏡膜層、及び、前記銀鏡膜層の表面に形成された上塗り塗膜、を有する銀鏡膜層が形成されたゴム弾性体であって、前記下塗り塗膜及び前記上塗り塗膜は、ポリオール成分を含む主材とポリイソシアネート成分を含む硬化剤とで形成された、それぞれの伸び率が８０％以上６００％以下である弾性ポリウレタン樹脂塗膜からなることを特徴とする。 The rubber elastic body in which the silver mirror film layer of the first aspect of the present invention is formed is an undercoat film formed on the surface of the rubber elastic body, a silver mirror film layer formed on the surface of the undercoat film, and the above A rubber elastic body having a silver mirror film layer formed on the surface of the silver mirror film layer, wherein the undercoat film and the top coat film are a main material containing a polyol component and a polyisocyanate component. It consists of the elastic polyurethane resin coating film formed with the hardening | curing agent containing these and each elongation rate is 80% or more and 600% or less.
係る態様の銀鏡膜層が形成されたゴム弾性体によれば、下塗り塗膜及び上塗り塗膜の伸び率が良好であるため、銀鏡膜層もそれにつれて変形性が良好となり、鏡面外観、付着性、耐屈曲性、耐寒屈曲性、冷熱繰り返し性等に優れた銀鏡膜層が形成されたゴム弾性体が得られる。なお、本発明における伸び率は、ＪＩＳＫ７３１１に準拠する方法によって測定した数値を示す。また、塗膜の伸び率が８０％未満の場合は、基材の変形に対する塗膜の追随性が低下し、亀裂を生じたり、基材との間の密着性が低下するようになる。さらに、塗膜の伸び率が６００％を越える場合は、塗膜が柔らかすぎて傷付きやすくなるとともに耐薬品性も低下するため、特に上塗り塗料の溶剤アタックなどで鏡面外観が低下する。より好ましい下塗り塗膜及び上塗り塗膜の伸び率は、１００％以上５００％以下である。 According to the rubber elastic body in which the silver mirror film layer of this aspect is formed, since the elongation rate of the undercoat film and the topcoat film is good, the deformability of the silver mirror film layer is improved accordingly, and the mirror appearance and adhesion Thus, it is possible to obtain a rubber elastic body on which a silver mirror film layer having excellent bending resistance, cold bending resistance, and thermal repeatability is formed. In addition, the elongation rate in this invention shows the numerical value measured by the method based on JISK7311. Moreover, when the elongation rate of a coating film is less than 80%, the followability of the coating film with respect to a deformation | transformation of a base material will fall, a crack will be produced, or adhesiveness between base materials will come to fall. Further, when the elongation percentage of the coating film exceeds 600%, the coating film is too soft and easily damaged, and the chemical resistance is also lowered, so that the mirror surface appearance is deteriorated particularly by a solvent attack of the top coating material. The elongation ratio of the more preferable undercoat film and topcoat film is 100% or more and 500% or less.
しかも、係る態様の銀鏡膜層が形成されたゴム弾性体によれば、弾性ポリウレタン樹脂塗膜は、透明性が良好で、耐熱性、耐溶剤性、耐酸性及び耐アルカリ性にも優れているため、上述した特性以外にも耐熱性、耐溶剤性、耐酸性及び耐アルカリ性にも優れた特性を示す銀鏡膜層が形成されたゴム弾性体が得られる。 Moreover, according to the rubber elastic body in which the silver mirror film layer of such an aspect is formed, the elastic polyurethane resin coating film has good transparency and is excellent in heat resistance, solvent resistance, acid resistance and alkali resistance. In addition to the above-described characteristics, a rubber elastic body on which a silver mirror film layer having excellent heat resistance, solvent resistance, acid resistance, and alkali resistance is formed can be obtained.
また、本発明の第２の態様の銀鏡膜層が形成されたゴム弾性体は、第１の態様の銀鏡膜層が形成されたゴム弾性体において、前記主材中にポリカプロラクトンポリオールからなる反応性軟化剤が含有されていることを特徴とする。 Further, the rubber elastic body in which the silver mirror film layer of the second aspect of the present invention is formed is a reaction comprising a polycaprolactone polyol in the main material in the rubber elastic body in which the silver mirror film layer of the first aspect is formed. A characteristic softener is contained.
かかる態様の銀鏡膜層が形成されたゴム弾性体によれば、主材中の反応性軟化剤の含有割合を変えることにより、下塗り塗膜ないし上塗り塗膜を形成する弾性ポリウレタン樹脂塗膜の伸び率を適宜に最適な値となるように制御することができるようになる。 According to the rubber elastic body in which the silver mirror film layer of this aspect is formed, the elongation of the elastic polyurethane resin coating film forming the undercoat film or the topcoat film can be changed by changing the content ratio of the reactive softener in the main material. It becomes possible to control the rate appropriately to an optimal value.
また、本発明の第３の態様の銀鏡膜層が形成されたゴム弾性体は、第２の態様の銀鏡膜層が形成されたゴム弾性体において、前記反応性軟化剤の含有割合は前記主材１００質量部に対して５〜１０質量部であることを特徴とする。 The rubber elastic body formed with the silver mirror film layer according to the third aspect of the present invention is the rubber elastic body formed with the silver mirror film layer according to the second aspect, wherein the content ratio of the reactive softening agent is the main content. It is 5-10 mass parts with respect to 100 mass parts of materials, It is characterized by the above-mentioned.
係る態様の銀鏡膜層が形成されたゴム弾性体によれば、下塗り塗膜ないし上塗り塗膜を形成する弾性ポリウレタン樹脂塗膜の伸び率を８０％以上６００％以下の範囲に適切にコントロールすることができるようになる。なお、主材中の反応性軟化剤の含有割合が５質量部未満であると、その含有割合が低くなるにしたがって下塗り塗膜ないし上塗り塗膜を形成する弾性ポリウレタン樹脂塗膜が硬質となって伸び率が８０％未満となってしまう。また、主材中の反応性軟化剤の含有割合が１０質量部を越えると、その含有割合が多くなるにしたがって塗膜形成用の主要成分であるポリオール成分の含有割合が少なくなるので弾性ポリウレタン樹脂塗膜の強度が低下する。 According to the rubber elastic body in which the silver mirror film layer of this aspect is formed, the elongation percentage of the elastic polyurethane resin coating film forming the undercoat film or the topcoat film is appropriately controlled within the range of 80% to 600%. Will be able to. If the content of the reactive softener in the main material is less than 5 parts by mass, the elastic polyurethane resin coating film forming the undercoat film or the topcoat film becomes hard as the content ratio decreases. The elongation is less than 80%. In addition, when the content ratio of the reactive softener in the main material exceeds 10 parts by mass, the content ratio of the polyol component, which is a main component for coating film formation, decreases as the content ratio increases, so that the elastic polyurethane resin The strength of the coating film decreases.
また、本発明の第４の態様の銀鏡膜層が形成されたゴム弾性体は、第１〜第３のいずれかの態様の銀鏡膜層が形成されたゴム弾性体において、前記硬化剤は弾性型ポリイソシアネートを含むことを特徴とする。 Moreover, the rubber elastic body in which the silver mirror film layer of the 4th aspect of this invention was formed is a rubber elastic body in which the silver mirror film layer of any one of the 1st-3rd aspect was formed, The said hardening | curing agent is elastic. Type polyisocyanate.
かかる態様の銀鏡膜層が形成されたゴム弾性体によれば、下塗り塗膜ないし上塗り塗膜を形成する弾性ポリウレタン樹脂塗膜の伸び率を適宜に最適な値となるように制御することができるようになる。係る態様においては、ポリウレタン樹脂塗膜の主材中に反応性軟化剤が含まれていてもよく、その場合は弾性ポリウレタン樹脂塗膜中の反応性軟化剤及び弾性ポリイソシアネートの両者の含有割合を適切に変えることにより、容易に下塗り塗膜ないし上塗り塗膜を形成する弾性ポリウレタン樹脂塗膜の伸び率を適切な範囲にコントロールすることができるようになる。 According to the rubber elastic body in which the silver mirror film layer of this aspect is formed, the elongation percentage of the elastic polyurethane resin coating film forming the undercoat film or the topcoat film can be controlled to an appropriate value as appropriate. It becomes like this. In such an embodiment, the reactive softener may be contained in the main material of the polyurethane resin coating film, and in that case, the content ratio of both the reactive softening agent and the elastic polyisocyanate in the elastic polyurethane resin coating film is set. By appropriately changing, it becomes possible to easily control the elongation ratio of the elastic polyurethane resin coating film that forms the undercoat film or the topcoat film within an appropriate range.
また、本発明の第５の態様の銀鏡膜層が形成されたゴム弾性体は、第１〜第４のいずれかの態様の銀鏡膜層が形成されたゴム弾性体において、前記ゴム弾性体と前記下塗り塗膜の間には接着用プライマー層が形成されていることを特徴とする。 The rubber elastic body in which the silver mirror film layer according to the fifth aspect of the present invention is formed is the rubber elastic body in which the silver mirror film layer according to any one of the first to fourth aspects is formed. An adhesive primer layer is formed between the undercoat coating films.
かかる態様の銀鏡膜層が形成されたゴム弾性体によれば、ゴム弾性体が軟質で塗膜の付着性が低いものであっても、接着用プライマー層の作用によってゴム弾生体と下塗り塗膜との間の接着性が良好となるので、銀鏡膜層が形成されたゴム弾性体の各種物性が良好となる。 According to the rubber elastic body in which the silver mirror film layer of this embodiment is formed, even if the rubber elastic body is soft and the adhesion of the coating film is low, the rubber elastic body and the undercoating film are formed by the action of the primer layer for adhesion. Therefore, various physical properties of the rubber elastic body on which the silver mirror film layer is formed are good.
また、本発明の第６の態様の銀鏡膜層が形成されたゴム弾性体は、第１〜第５のいずれかの態様の銀鏡膜層が形成されたゴム弾性体において、前記銀鏡膜層中には弾性型ポリイソシアネートで表面がウレタン化されたコロイダルシリカが含有されていることを特徴とする。 The rubber elastic body in which the silver mirror film layer of the sixth aspect of the present invention is formed is the rubber elastic body in which the silver mirror film layer of any one of the first to fifth aspects is formed. Is characterized in that it contains colloidal silica whose surface is urethaned with an elastic polyisocyanate.
かかる態様の銀鏡膜層が形成されたゴム弾性体によれば、下塗り塗膜及び上塗り塗膜がともにポリウレタン樹脂塗膜であることと相まって、銀鏡膜層と下塗り塗膜との間及び銀鏡膜層と上塗り塗膜との間の密着性がそれぞれ向上し、また、銀粒子間の緩衝作用が良好になるので、銀鏡膜層の変形追従性が改善され、良好な物性を有する銀鏡膜層が形成されたゴム弾性体が得られる。 According to the rubber elastic body in which the silver mirror film layer of this aspect is formed, the undercoat film and the topcoat film are both polyurethane resin paint films, and between the silver mirror film layer and the undercoat film film and the silver mirror film layer. Adhesion between the coating film and the top coat film is improved, and the buffering action between the silver particles is improved, so that the deformation followability of the silver mirror film layer is improved, and a silver mirror film layer having good physical properties is formed. A rubber elastic body is obtained.
さらに、本発明の第７の態様のゴム弾性体の表面に銀鏡膜層を形成する方法は、
ゴム弾性体の表面に下塗り塗料を塗布して下塗り塗膜を形成する工程と、
前記下塗り塗膜の表面に銀鏡膜層形成用液を塗布して銀鏡膜層を形成する工程と、
前記銀鏡膜層の表面に上塗り塗料を塗布して上塗り塗膜を形成する工程と、
を備える、ゴム弾性体の表面に銀鏡膜層を形成する方法であって、
前記下塗り塗料及び前記上塗り塗料として、それぞれポリオール成分を含む主材とポリイソシアネート成分を含む硬化剤とを含み、前記下塗り塗膜及び前記上塗り塗膜がそれぞれ伸び率８０％以上６００％以下の弾性ポリウレタン樹脂塗膜となるものを用いることを特徴とする。
Furthermore, the method for forming a silver mirror film layer on the surface of the rubber elastic body according to the seventh aspect of the present invention includes:
Applying an undercoat paint to the surface of the rubber elastic body to form an undercoat film;
Applying a silver mirror film layer forming solution to the surface of the undercoat coating film to form a silver mirror film layer;
Forming a top coat film by applying a top coat to the surface of the silver mirror film layer;
A method of forming a silver mirror film layer on the surface of a rubber elastic body,
The undercoat paint and the top coat paint each include a main component containing a polyol component and a curing agent containing a polyisocyanate component, and the undercoat paint film and the top coat paint each have an elongation of 80% or more and 600% or less. A resin coating film is used.
また、本発明の第８の態様のゴム弾性体の表面に銀鏡膜層を形成する方法は、第７の態様のゴム弾性体の表面に銀鏡膜層を形成する方法において、前記下塗り塗料及び上塗り塗料として、前記主材中にポリカプロラクトンポリオールからなる反応性軟化剤を含むものを用いることを特徴とする。 The method of forming the silver mirror film layer on the surface of the rubber elastic body according to the eighth aspect of the present invention is the method of forming a silver mirror film layer on the surface of the rubber elastic body according to the seventh aspect. As the coating material, a material containing a reactive softener made of polycaprolactone polyol in the main material is used.
また、本発明の第９の態様のゴム弾性体の表面に銀鏡膜層を形成する方法は、第８の態様のゴム弾性体の表面に銀鏡膜層を形成する方法において、前記反応性軟化剤の含有割合が主材１００質量部に対して５〜１０質量部のものを用いることを特徴とする。 The method for forming a silver mirror film layer on the surface of the rubber elastic body according to the ninth aspect of the present invention is the method for forming a silver mirror film layer on the surface of the rubber elastic body according to the eighth aspect. The content ratio is 5 to 10 parts by mass with respect to 100 parts by mass of the main material.
また、本発明の第１０の態様のゴム弾性体の表面に銀鏡膜層を形成する方法は、第７〜９のいずれかの態様のゴム弾性体の表面に銀鏡膜層を形成する方法において、前記硬化剤として弾性型ポリイソシアネートを含むものを用いることを特徴とする。 The method for forming a silver mirror film layer on the surface of the rubber elastic body according to the tenth aspect of the present invention is the method for forming a silver mirror film layer on the surface of the rubber elastic body according to any one of the seventh to ninth aspects. A material containing elastic polyisocyanate is used as the curing agent.
また、本発明の第１１の態様のゴム弾性体の表面に銀鏡膜層を形成する方法は、第７〜第１０のいずれかの態様のゴム弾性体の表面に銀鏡膜層を形成する方法において、前記ゴム弾性体の表面に接着用プライマー層を形成し、前記接着用プライマー層の表面に前記下塗り塗料を塗布して下塗り塗層を形成することを特徴とする。 The method for forming a silver mirror film layer on the surface of the rubber elastic body according to the eleventh aspect of the present invention is the method for forming a silver mirror film layer on the surface of the rubber elastic body according to any of the seventh to tenth aspects. A primer layer for adhesion is formed on the surface of the rubber elastic body, and the primer layer is formed by applying the primer coating on the surface of the primer layer for adhesion.
また、本発明の第１２の態様のゴム弾性体の表面に銀鏡膜層を形成する方法は、第７〜１１のいずれかの態様のゴム弾性体の表面に銀鏡膜層を形成する方法において、前記銀鏡膜層形成用液中に弾性型ポリイソシアネートで表面がウレタン化されたコロイダルシリカが含有されているものを用いることを特徴とする。 The method for forming a silver mirror film layer on the surface of the rubber elastic body according to the twelfth aspect of the present invention is the method for forming a silver mirror film layer on the surface of the rubber elastic body according to any one of the seventh to eleventh aspects. The silver mirror film layer forming liquid is characterized in that it contains colloidal silica whose surface is urethanized with an elastic polyisocyanate.
本発明の第７〜第１２の態様のゴム弾性体の表面に銀鏡膜層を形成する方法によれば、それぞれ本発明の第１〜第６の態様の銀鏡膜層が形成されたゴム弾性体を製造することができるようになる。 According to the method of forming the silver mirror film layer on the surface of the rubber elastic body according to the seventh to twelfth aspects of the present invention, the rubber elastic body formed with the silver mirror film layer according to the first to sixth aspects of the present invention, respectively. Can be manufactured.
以上述べたように、本発明によれば、鏡面外観、付着性、耐屈曲性、耐寒屈曲性、冷熱繰り返し性、さらには、透明性が良好で、耐熱性、耐溶剤性、耐酸性及び耐アルカリ性にも優れた銀鏡膜層が形成されたゴム弾性体が得られる。 As described above, according to the present invention, the mirror appearance, adhesion, bending resistance, cold bending resistance, cold repeatability, and transparency are good, and heat resistance, solvent resistance, acid resistance and resistance are good. A rubber elastic body having a silver mirror film layer excellent in alkalinity is obtained.
以下、本発明に係る銀鏡膜層が形成されたゴム弾性体の構成及びその製造方法について、各種実験例を用いて詳細に説明する。ただし、以下に示す各種実験例は、本発明の技術思想を具体化するための例を示すものであって、本発明をこれらの実験例に示したものに特定することを意図するものではない。本発明は特許請求の範囲に含まれるその他の実施形態のものにも等しく適応し得るものである。 Hereinafter, the structure of the rubber elastic body in which the silver mirror film layer according to the present invention is formed and the manufacturing method thereof will be described in detail using various experimental examples. However, the following various experimental examples show examples for embodying the technical idea of the present invention, and are not intended to specify the present invention to those shown in these experimental examples. . The invention is equally applicable to other embodiments within the scope of the claims.
なお、本発明の各種実施形態で使用することができるゴム弾性体素材としては、天然ゴム（ＮＲ）、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、イソプレンゴム（ＩＲ）などの汎用ゴムの他、耐熱性、耐油性や耐候性などの高性能が要求される用途には、ニトリルゴム（ＮＢＲ）、エチレンプロピレンゴム（ＥＰＤＭ）、アクリルゴム（ＡＣＭ）、シリコーンゴム（ＶＭＱ）やフッ素ゴム（ＦＫＭ）などを使用することができる。また、プラスチックと加硫ゴムの隙間を埋める形態として熱可塑性エラストマー（ＴＰＥ）があり、ポリオレフィン系、ポリスチレン系、ポリエステル系やポリウレタン系などのＴＰＥも用いることができる。さらに、エチレン酢酸ビニル（ＥＶＡ）や軟質塩化ビニルなどの軟質プラスチックに対しても、適用可能である。 The rubber elastic material that can be used in various embodiments of the present invention includes natural rubber (NR), butadiene rubber (BR), styrene butadiene rubber (SBR), isoprene rubber (IR), and other general-purpose rubbers. Other applications that require high performance such as heat resistance, oil resistance, and weather resistance include nitrile rubber (NBR), ethylene propylene rubber (EPDM), acrylic rubber (ACM), silicone rubber (VMQ), and fluoro rubber ( FKM) can be used. Moreover, there exists a thermoplastic elastomer (TPE) as a form which fills the gap between plastic and vulcanized rubber, and TPE such as polyolefin, polystyrene, polyester and polyurethane can also be used. Furthermore, it is applicable also to soft plastics, such as ethylene vinyl acetate (EVA) and soft vinyl chloride.
１液系のゴム用塗料としては、ゴムにビニルモノマーを反応させたグラフトゴム系塗料、高伸度のポリウレタン樹脂又はアクリル樹脂などの１液溶剤型塗料、アクリルゴム、ポリウレタンエマルションを主成分とする１液水性塗料も実用化されている。しかし、耐候性や繰り返し変形に対する追随耐久性などの性能面より、高強度高伸度タイプのポリオール／ポリイソシアネート系や更に鎖延長剤に低分子量ジアミンを使用したポリウレタン系塗料を用いることが好ましい。 As a one-component rubber paint, a main component is a graft rubber-based paint obtained by reacting rubber with a vinyl monomer, a one-component solvent-type paint such as a high-stretch polyurethane resin or an acrylic resin, acrylic rubber, and a polyurethane emulsion. One-component water-based paints are also in practical use. However, it is preferable to use a high-strength, high-elongation type polyol / polyisocyanate system or a polyurethane-based paint using a low molecular weight diamine as a chain extender from the viewpoint of performance such as weather resistance and durability against repeated deformation.
２液系のゴム用塗料としては、ポリウレタンウレア系の樹脂を主成分とした２液硬化型高性能タイプのポリウレタン系塗料が望ましい。ポリオールとしては、ポリエステル系、ポリカーボネート系、ポリエーテル系、アクリル系およびフッ素系ポリオールを使用することができる。硬化剤に関しては、イソシアネート誘導体はビウレットタイプ、イソシアヌレートタイプ、アダクトタイプなどの標準型や、弾性型ポリイソシアネート（ベースポリイソシアネートをポリエーテルポリオールなどでウレタン化させた変性ポリイソシアネート）を選択することができる。必要な塗膜の性能面や施行性の点から、この硬化剤を適宜に使い分ければよい。なお、ポリオールと硬化剤の使用比率は、ポリオールのＯＨ価と硬化剤のＮＣＯ％で決まり、通常はモル比１±０．２の範囲で使用される。 As the two-component rubber paint, a two-component curing type high-performance polyurethane-based paint mainly composed of a polyurethane urea-based resin is desirable. As the polyol, polyester-based, polycarbonate-based, polyether-based, acrylic-based and fluorine-based polyols can be used. For the curing agent, the isocyanate derivative can be selected from standard types such as biuret type, isocyanurate type, adduct type, and elastic polyisocyanate (modified polyisocyanate obtained by urethanizing base polyisocyanate with polyether polyol). it can. What is necessary is just to use this hardening | curing agent properly from the point of the performance surface of a required coating film, or the point of enforcement. The use ratio of the polyol and the curing agent is determined by the OH number of the polyol and the NCO% of the curing agent, and is usually used in a molar ratio of 1 ± 0.2.
また、銀鏡膜層形成液は、特許文献１（特許第５６１０３５９号公報）及び特許文献３（特許第５９５０４２７号公報）に記載された方法により製造したものを適宜に選択して使用した。さらに、各実験例におけるスプレー塗装に際しては、全て同一の条件となるように統一して、実質的に同一の塗装厚さとなるようにした。 Further, as the silver mirror film layer forming liquid, those prepared by the methods described in Patent Document 1 (Patent No. 5610359) and Patent Document 3 (Patent No. 5950427) were appropriately selected and used. Furthermore, the spray coating in each experimental example was unified so that all the same conditions were obtained, so that the coating thickness was substantially the same.
各実験例で作成した銀鏡膜層が形成されたゴム弾性体の断面図を図１に示した。この銀鏡膜層が形成されたゴム弾性体１０は、基体としてのゴム弾性体１１と、このゴム弾性体１１の表面に形成された下塗り塗膜１２と、下塗り塗膜１２の表面に形成された銀鏡膜層１３と、銀鏡膜層１３の表面に形成された上塗り塗膜１４と、を備えている。以下では、各実験例について、ゴム弾性体１１、下塗り塗膜１２、銀鏡膜層１３及び上塗り塗膜１４について、主として製造方法によって具体的に説明する。
A cross-sectional view of the rubber elastic body formed with the silver mirror film layer prepared in each experimental example is shown in FIG. The rubber
［実験例１］
（下塗り塗膜）
アクリルポリオール樹脂（コータックスＬＨ６０１、固形分５０％、ＯＨ価２０、東レ・ファインケミカル（株））８０質量部に酢酸ブチル２０質量部を撹拌しながら均一に混合した。さらに、反応性軟化剤としてのポリカプロラクトントリオール（プラクセル３０８、（株）ダイセル有機合成カンパニー）を１０質量部、硬化触媒としてジラウリル酸−ジ−ｎ−ブチルスズを０．０１質量部、レベラー（ＢＹＫ３００、ビックケミー・ジャパン）を０．２質量部添加混合して、下塗り塗料の主剤を調製した。次いで、アダクトタイプのポリイソシアネート硬化剤（コロネートＨＬ、固形分７５％、ＮＣＯ１２．３〜１３．３％、日本ポリウレタン工業（株））を、主剤：硬化剤＝１００：１０（質量比）の割合で混合し、シンナーで希釈し、黒色の天然ゴムシートにスプレー塗装した。次いで、９０〜１００℃で４０分間強制乾燥し、下塗り塗膜が形成された天然ゴムシートを得た。
[Experimental Example 1]
(Undercoat)
20 parts by mass of butyl acetate was uniformly mixed with 80 parts by mass of acrylic polyol resin (Cotax LH601, solid content 50%, OH number 20, Toray Fine Chemical Co., Ltd.). Furthermore, 10 parts by mass of polycaprolactone triol (Placcel 308, Daicel Organic Synthesis Company) as a reactive softening agent, 0.01 parts by mass of dilauric acid-di-n-butyltin as a curing catalyst, leveler (BYK300, Big Chemie Japan) was added and mixed in an amount of 0.2 parts by mass to prepare a base material for an undercoat. Next, adduct type polyisocyanate curing agent (Coronate HL, solid content 75%, NCO 12.3-13.3%, Nippon Polyurethane Industry Co., Ltd.), ratio of main agent: curing agent = 100: 10 (mass ratio) And diluted with thinner and spray-coated on a black natural rubber sheet. Subsequently, it forcedly dried at 90-100 degreeC for 40 minutes, and obtained the natural rubber sheet in which the primer coating film was formed.
（銀鏡膜層）
銀鏡膜層形成液を、上記特許文献３（特許第５９５０４２７号公報）の［実験例１］に記載の方法により調製した。すなわち、高分子分散剤としてＤｉｓｐｅｒｂｙｋ２０１５（不揮発分４０％、酸価１０、ＢＹＫ社）４ｇを２−プロパノール（イソプロピルアルコール）１００ｇ中に溶解し、酸化銀粉末２５ｇを懸濁させた。この高分子分散剤の不揮発分の酸価は２５であり、高分子分散剤の含有割合は酸化銀に対して質量比で（４×０．４／２５）×１００＝６．４％となる。なお、Ｄｉｓｐｅｒｂｙｋ２０１５は、スチレン−無水マレイン酸樹脂構造を有し、この無水マレイン酸の一部が末端水酸基のポリアルキレングリコールによって変性されたものからなる。
(Silver mirror film layer)
A silver mirror film layer forming solution was prepared by the method described in [Experimental Example 1] of Patent Document 3 (Patent No. 5950427). That is, 4 g of Disperbyk 2015 (nonvolatile content 40%,
次いで、この懸濁液に超音波装置Ｈ３ ６５０（（有）カワジリマシナリー社製）を使用して、１５〜１７℃の室温下で２時間、２０ＫＨｚで照射した。次に１μｍのフィルターでろ過して褐色の銀ナノ粒子分散液を得た。この銀ナノ粒子分散液をエチルアルコールで４倍に希釈してスプレー塗装し、常温下で１時間乾燥して下塗り塗膜上に銀鏡膜層が形成された天然ゴムシートを得た。 Subsequently, this suspension was irradiated at 20 KHz at room temperature of 15 to 17 ° C. for 2 hours using an ultrasonic device H3 650 (manufactured by Kawaji Re-Machinery). Next, it filtered with a 1 micrometer filter and the brown silver nanoparticle dispersion liquid was obtained. This silver nanoparticle dispersion was diluted 4-fold with ethyl alcohol, spray-coated, and dried at room temperature for 1 hour to obtain a natural rubber sheet having a silver mirror film layer formed on the undercoat film.
（上塗り塗膜）
上記の実験例１の下塗り塗料をそのまま上塗り塗料として使用してスプレー塗装し、９０〜１００℃で４０分間乾燥し、天然ゴムシートの表面に下塗り塗膜、銀鏡膜層及び上塗り塗膜が形成された実験例１の銀鏡膜層形成試料を得た。
(Top coat)
Spray coating is performed using the undercoating paint of Experimental Example 1 as it is as an overcoating paint, followed by drying at 90 to 100 ° C. for 40 minutes to form an undercoating film, a silver mirror film layer and an overcoating film on the surface of the natural rubber sheet. A silver mirror film layer-forming sample of Experimental Example 1 was obtained.
［実験例２］
（下塗り塗膜）
アクリルポリオール樹脂（コータックスＬＨ６０１）を８０質量部に酢酸ブチル２０質量部を撹拌しながら均一に混合した。次に、触媒としてジラウリル酸−ジ−ｎ−ブチルスズ０．０１質量部、レベラー（ＢＹＫ３００）を０．２質量部添加混合して、下塗り塗料の主剤を調製した。次に、弾性型ポリイソシアネート硬化剤（デュラネートＥ４０５−７０Ｂ、固形分７０％、ＮＣＯ６．２％、旭化成（株））を、主剤：硬化剤＝１００：１５（質量比）となるように混合し、シンナーで希釈して黒色の天然ゴムシートにスプレー塗装した。次いで、９０〜１００℃で４０分間強制乾燥して下塗り塗膜が形成された天然ゴムシートを得た。
[Experiment 2]
(Undercoat)
An acrylic polyol resin (Cotax LH601) was uniformly mixed with 80 parts by mass of 20 parts by mass of butyl acetate. Next, 0.01 parts by mass of dilauric acid-di-n-butyltin and 0.2 parts by mass of a leveler (BYK300) were added and mixed as a catalyst to prepare a base material for an undercoat paint. Next, an elastic polyisocyanate curing agent (Duranate E405-70B, solid content 70%, NCO 6.2%, Asahi Kasei Co., Ltd.) is mixed so that the main agent: curing agent = 100: 15 (mass ratio). It was diluted with thinner and spray-coated on a black natural rubber sheet. Subsequently, it forcedly dried at 90-100 degreeC for 40 minutes, and obtained the natural rubber sheet in which the undercoat film was formed.
（銀鏡膜層）
銀鏡膜層は、実験例１の場合と同様にして形成した。
(Silver mirror film layer)
The silver mirror film layer was formed in the same manner as in Experimental Example 1.
（上塗り塗膜）
実験例２の下塗り塗料をそのまま上塗り塗料として使用してスプレー塗装後、９０〜１００℃で４０分間乾燥し、天然ゴムシートの表面に下塗り塗膜、銀鏡膜層及び上塗り塗膜が形成された実験例２の銀鏡膜層形成試料を得た。
(Top coat)
Experimental Example 2 An experiment in which an undercoating film, a silver mirror film layer, and an overcoating film were formed on the surface of a natural rubber sheet after spray coating using the undercoating paint as it was as an overcoating paint and then drying at 90 to 100 ° C. for 40 minutes. The silver mirror film layer formation sample of Example 2 was obtained.
［実験例３］
（下塗り塗膜）
実験例１と同様の下塗り塗料の主剤に対し、弾性型ポリイソシアネート硬化剤（デュラネートＥ４０５−７０Ｂ）を、主剤：硬化剤＝１００：２０（質量比）となるように混合し、シンナーで希釈して黒色の天然ゴムシートにスプレー塗装した。次いで、９０〜１００℃で４０分間強制乾燥して下塗り塗膜が形成された天然ゴムシートを得た。
[Experiment 3]
(Undercoat)
An elastic polyisocyanate curing agent (Duranate E405-70B) is mixed with the main component of the undercoat similar to Experimental Example 1 so that the main component: curing agent = 100: 20 (mass ratio), and diluted with thinner. Sprayed on a black natural rubber sheet. Subsequently, it forcedly dried at 90-100 degreeC for 40 minutes, and obtained the natural rubber sheet in which the undercoat film was formed.
（銀鏡膜層）
銀鏡膜層は、実験例１の場合と同様にして形成した。
(Silver mirror film layer)
The silver mirror film layer was formed in the same manner as in Experimental Example 1.
（上塗り塗膜）
実験例３の下塗り塗料をそのまま上塗り塗料として使用してスプレー塗装後、９０〜１００℃で４０分間乾燥し、天然ゴムシートの表面に下塗り塗膜、銀鏡膜層及び上塗り塗膜が形成された実験例３の銀鏡膜層形成試料を得た。
(Top coat)
Experimental Example 3 An experiment in which an undercoat paint, a silver mirror film layer, and a top coat film were formed on the surface of a natural rubber sheet after spray coating using the undercoat paint as it is as an overcoat paint and then drying at 90 to 100 ° C. for 40 minutes. A silver mirror film layer-forming sample of Example 3 was obtained.
［実験例４］
（下塗り塗膜）
ポリカーボネートポリオール樹脂（デュラノールＴ５６５２、固形分１００％、ＯＨ価５１〜６１、旭化成ケミカルズ（株））６０質量部に酢酸ブチル４０質量部を撹拌しながら均一に混合した。さらに、反応性軟化剤としてのポリカプロラクトントリオール（プラクセル３０８）を６質量部、触媒としてジラウリル酸−ジ−ｎ−ブチルスズ０．０２質量部、レベラー（ＢＹＫ３００）を０．２質量部添加混合して、下塗り塗料の主剤を調製した。次に、硬化剤として、ビウレット型ポリイソシアネート（デュラネート２４Ａ−１００、固形分１００％、ＮＣＯ２３．５％、旭化成（株））を、主剤：硬化剤＝１００：１０（質量比）となる割合で混合し、シンナーで希釈して、黒色のブチルゴムシートにスプレー塗装した。次いで、９０〜１００℃で４０分間強制乾燥して下塗り塗膜が形成されたブチルゴムシートを得た。
[Experimental Example 4]
(Undercoat)
40 parts by mass of butyl acetate was uniformly mixed with 60 parts by mass of a polycarbonate polyol resin (Duranol T5652, solid content 100%, OH number 51 to 61, Asahi Kasei Chemicals Corporation). Furthermore, 6 parts by mass of polycaprolactone triol (Placcel 308) as a reactive softening agent, 0.02 parts by mass of dilauric acid-di-n-butyltin as a catalyst, and 0.2 parts by mass of a leveler (BYK300) were added and mixed. The main component of the undercoat paint was prepared. Next, biuret type polyisocyanate (Duranate 24A-100, solid content 100%, NCO 23.5%, Asahi Kasei Co., Ltd.) is used as a curing agent at a ratio of main agent: curing agent = 100: 10 (mass ratio). The mixture was mixed, diluted with thinner, and spray-coated on a black butyl rubber sheet. Subsequently, it was forcibly dried at 90 to 100 ° C. for 40 minutes to obtain a butyl rubber sheet on which an undercoat coating film was formed.
（銀鏡膜層）
銀鏡膜層形成液を、上記特許文献１（特許第５６１０３５９号公報）の［実験例１］に記載の方法により調製した。すなわち、２−エチルヘキシルアンモニウム ２−エチルヘキシルカルバメート４．１６ｇに、２−プロパノール（イソプロピルアルコール）（大伸化学（株））１０．０ｇを混合した溶液に、酸化銀（Ａｇ２Ｏ）（石福金属工業（株））２．１ｇを添加し、常温で２時間撹拌した。この溶液は、最初は黒色の懸濁液であったが、やがて灰白色に濁った２−エチルヘキシルアンモニウム ２−エチルヘキシルカルバメート酸化銀錯体を含む２−プロパノール溶液になった。灰白色に濁った成分は未反応の酸化銀粒子であり、２−エチルヘキシルアンモニウム ２−エチルヘキシルカルバメート酸化銀錯体は２−プロパノールに溶解した状態となっている。その後、２−エチルヘキシルアンモニウム ２−エチルヘキシルカルバメート酸化銀錯体を含む２−プロパノール溶液中に沈降している酸化銀を濾過して除去した。
(Silver mirror film layer)
A silver mirror film layer forming solution was prepared by the method described in [Experimental Example 1] of Patent Document 1 (Japanese Patent No. 5610359). That is, to a solution obtained by mixing 10.0 g of 2-propanol (isopropyl alcohol) (Daishin Chemical Co., Ltd.) with 4.16 g of 2-ethylhexyl ammonium 2-ethylhexyl carbamate, silver oxide (Ag 2 O) (Ishifuku Metal) 2.1 g of Kogyo Co., Ltd. was added and stirred at room temperature for 2 hours. This solution was initially a black suspension, but eventually became a 2-propanol solution containing 2-ethylhexylammonium 2-ethylhexylcarbamate silver oxide complex which became cloudy white. The component which became grayish white is unreacted silver oxide particles, and 2-ethylhexylammonium 2-ethylhexylcarbamate silver oxide complex is in a state dissolved in 2-propanol. Thereafter, silver oxide precipitated in 2-propanol solution containing 2-ethylhexylammonium 2-ethylhexylcarbamate silver oxide complex was removed by filtration.
別途、ｎ−ブチルアミン（和光純薬（株））１．９３ｇに２−プロパノール（大伸化学（株））６．０ｇを混合した溶液に、酸化銀（石福金属工業（株））０．９ｇを添加し、常温で３０分間撹拌し、ｎ−ブチルアミン酸化銀錯体を調製した。このｎ−ブチルアミン酸化銀錯体は、２−プロパノール中で黒色の懸濁液となり、その後、２−プロパノールには溶解せずに沈降した。 Separately, in a solution obtained by mixing 6.03 g of 2-propanol (Daishin Chemical Co., Ltd.) with 1.93 g of n-butylamine (Wako Pure Chemical Industries, Ltd.), 0. 9 g was added and stirred at room temperature for 30 minutes to prepare an n-butylamine silver oxide complex. This n-butylamine silver oxide complex became a black suspension in 2-propanol, and then settled without dissolving in 2-propanol.
上述のようにして調製した２−エチルヘキシルアンモニウム ２−エチルヘキシルカルバメート酸化銀錯体が溶解した２−プロパノール溶液とｎ−ブチルアミン酸化銀錯体が懸濁した２−プロパノール溶液とを混合し、撹拌した。この混合液は、次第に灰色の懸濁液となり、その後、透明な溶液になった。次に、この混合液に、室温では還元作用を示さず、室温を超えた温度で還元作用を示す還元剤であるＮ，Ｎ−ジメチルアミノエタノール（和光純薬（株））２．３３ｇを加え、２−プロパノールを加えて全量を３０ｇになるようにして、実験例４の酸化銀錯体用液からなる銀鏡膜層形成用組成液を調製した。 The 2-propanol solution in which the 2-ethylhexylammonium 2-ethylhexylcarbamate silver oxide complex prepared as described above was dissolved and the 2-propanol solution in which the n-butylamine silver oxide complex was suspended were mixed and stirred. The mixture gradually became a gray suspension and then became a clear solution. Next, 2.33 g of N, N-dimethylaminoethanol (Wako Pure Chemical Industries, Ltd.), which is a reducing agent that does not show a reducing action at room temperature but shows a reducing action at a temperature exceeding room temperature, is added to this mixed solution. The composition liquid for silver mirror film layer formation which consists of a liquid for silver oxide complexes of Experimental Example 4 was prepared by adding 2-propanol to a total amount of 30 g.
この銀鏡膜層形成用組成液を、２−プロパノールで３倍に希釈して下塗り塗料が形成された実験例４のブチルゴムシートの表面にスプレー塗装し、８０〜９０℃で３０分間乾燥して下塗り塗膜上に銀鏡膜層が形成されたブチルゴムシートを得た。 This silver mirror film layer-forming composition solution was spray-coated on the surface of the butyl rubber sheet of Experimental Example 4 which was diluted 3-fold with 2-propanol to form an undercoat and dried at 80 to 90 ° C. for 30 minutes to undercoat A butyl rubber sheet having a silver mirror film layer formed on the coating film was obtained.
（上塗り塗膜）
実験例４の下塗り塗料をそのまま上塗り塗料として使用してスプレー塗装後、９０〜１００℃で４０分間乾燥し、ブチルゴムシートの表面に下塗り塗膜、銀鏡膜層及び上塗り塗膜が形成された実験例４の銀鏡膜層形成試料を得た。
(Top coat)
Experimental Example 4 An experimental example in which an undercoating film, a silver mirror film layer, and an overcoating film were formed on the surface of a butyl rubber sheet after spray coating using the undercoating paint as it was as the top coating, and then drying at 90 to 100 ° C. for 40 minutes. 4 silver mirror film layer formation samples were obtained.
［実験例５］
（上塗り塗膜）
エチレンプロピレンゴム（ＥＰＤＭ）などのオレフィン系ゴム、オレフィン系熱可塑性エラストマー（ＴＰＯ）などの熱可塑性エラストマー、エチレン−酢酸ビニル共重合体樹脂、軟質ポリプロピレン樹脂（ＰＰ）などの軟質プラスチックは、難接着性であり、ワンコートが困難である。対策として、各種プライマーが市販されているが、変性ポリオレフィン系の接着用プライマーを用いることが好ましい。実験例５では、ＥＰＤＭ素材表面へ変性ポリオレフィン系の接着用プライマーを塗布し、この表面に下塗り塗膜、銀鏡膜層及び上塗り塗膜が形成された実験例５の銀鏡膜層形成試料を作成した。
[Experimental Example 5]
(Top coat)
Olefin rubbers such as ethylene propylene rubber (EPDM), thermoplastic elastomers such as olefin thermoplastic elastomer (TPO), soft plastics such as ethylene-vinyl acetate copolymer resin and soft polypropylene resin (PP) are difficult to adhere. And one coat is difficult. As a countermeasure, various primers are commercially available, but it is preferable to use a modified polyolefin-based adhesion primer. In Experimental Example 5, a modified polyolefin-based adhesion primer was applied to the surface of the EPDM material, and a silver mirror film layer-forming sample of Experimental Example 5 in which an undercoat film, a silver mirror film layer, and a topcoat film were formed on this surface was prepared. .
変性ポリオレフィン系プライマー（ユニストールＰ−４０１、固形分８％、三井化学（株））１００質量部にトルエン５０質量部を添加混合して接着用プライマーを調製した。この接着用プライマーを、実験例３で用いたのと同様の黒色の天然ゴムシートの表面にスプレー塗装し、常温乾燥１０分後に実験例３で調製した下塗り塗料を塗装した。次いで、９０〜１００℃で４０分間強制乾燥して下塗り塗膜が形成されたＥＰＤＭシートを得た。 A primer for adhesion was prepared by adding 50 parts by mass of toluene to 100 parts by mass of a modified polyolefin-based primer (Unistor P-401, solid content 8%, Mitsui Chemicals, Inc.). This adhesion primer was spray-coated on the surface of a black natural rubber sheet similar to that used in Experimental Example 3, and the primer coating prepared in Experimental Example 3 was applied after drying at room temperature for 10 minutes. Subsequently, it forcedly dried at 90-100 degreeC for 40 minutes, and obtained the EPDM sheet in which the primer coating film was formed.
（銀鏡膜層）
銀鏡膜層は、実験例４の場合と同様にして形成した。
(Silver mirror film layer)
The silver mirror film layer was formed in the same manner as in Experimental Example 4.
（上塗り塗膜）
実験例３の下塗り塗料をそのまま上塗り塗料として使用してスプレー塗装後、９０〜１００℃で４０分間乾燥し、ＥＰＤＭシートの表面に接着用プライマー層、下塗り塗膜、銀鏡膜層及び上塗り塗膜が形成された実験例５の銀鏡膜層形成試料を得た。
(Top coat)
The undercoat paint of Experimental Example 3 was used as it was as an overcoat paint, and after spray coating, it was dried at 90 to 100 ° C. for 40 minutes. The primer layer, the undercoat film, the silver mirror film layer and the overcoat film were adhered to the surface of the EPDM sheet. A silver mirror film layer-forming sample of Experimental Example 5 was obtained.
［実験例６］
（下塗り塗膜）
実験例３と同様にして、下塗り塗膜が形成された天然ゴムシートを得た。
[Experimental Example 6]
(Undercoat)
In the same manner as in Experimental Example 3, a natural rubber sheet on which an undercoat coating film was formed was obtained.
（銀鏡膜層）
有機溶媒分散コロイダルシリカ（平均粒子径１０〜１５ｎｍ、分散媒メチルイソブチルケトン（ＭＩＢＫ）、固形分３０％、日産化学工業（株））１００質量部に対して、弾性ポリイソシアネート（デュラネートＥ４０５−７０Ｂ）を３質量部添加し、窒素ガス気流中で撹拌しながら６０〜７０℃で５時間加熱した。反応終了後、２５℃〜３０℃で２４時間熟成して表面がウレタン化されたコロイダルシリカを得た。この反応は、以下の反応式に示すように、ナノシリカ表面のＳｉＯＨ基とポリイソシアネートのウレタン化反応と考えられる。
−ＳｉＯ２−ＯＨ ＋ ＯＣＮ…Ｒ…ＮＣＯ →
−ＳｉＯ２−ＣＯＯＮＨ…Ｒ…ＨＮＯＯＣ−ＳｉＯ２−
(Silver mirror film layer)
Elastic polyisocyanate (Duranate E405-70B) with respect to 100 parts by mass of organic solvent-dispersed colloidal silica (average particle size 10-15 nm, dispersion medium methyl isobutyl ketone (MIBK), solid content 30%, Nissan Chemical Industries, Ltd.) 3 parts by mass was added and heated at 60 to 70 ° C. for 5 hours while stirring in a nitrogen gas stream. After the completion of the reaction, the mixture was aged at 25 ° C. to 30 ° C. for 24 hours to obtain colloidal silica whose surface was urethanized. This reaction is considered to be a urethanization reaction between the SiOH group on the nanosilica surface and the polyisocyanate, as shown in the following reaction formula.
-SiO 2 -OH + OCN ... R ... NCO →
-SiO 2 -COONH ... R ... HNOOC- SiO 2 -
次に、実験例１と同様にして得た銀ナノ粒子分散液中に、この表面がウレタン化されたコロイダルシリカ液を不揮発分比で１２％添加混合して、褐色のナノ銀／ウレタン化シリカ複合粒子分散液を得た。このナノ銀／表面がウレタン化されたシリカ複合粒子分散液をエチルアルコールで４倍に希釈して下塗り塗膜が形成された天然ゴムシートの表面にスプレー塗装し、常温下で１時間乾燥して銀鏡膜層を形成させた。 Next, in the silver nanoparticle dispersion obtained in the same manner as in Experimental Example 1, this surface urethanized colloidal silica liquid was added and mixed in a non-volatile content ratio of 12% to obtain a brown nanosilver / urethanized silica. A composite particle dispersion was obtained. This nano silver / urethane-modified silica composite particle dispersion is diluted 4-fold with ethyl alcohol and spray-coated on the surface of a natural rubber sheet on which an undercoat film has been formed, and dried at room temperature for 1 hour. A silver mirror film layer was formed.
（上塗り塗膜）
実験例３の下塗り塗料をそのまま上塗り塗料として使用してスプレー塗装後、９０〜１００℃で４０分間乾燥し、天然ゴムシートの表面に下塗り塗膜、銀鏡膜層及び上塗り塗膜が形成された実験例６の銀鏡膜層形成試料を得た。
(Top coat)
Experimental Example 3 An experiment in which an undercoat paint, a silver mirror film layer, and a top coat film were formed on the surface of a natural rubber sheet after spray coating using the undercoat paint as it is as an overcoat paint and then drying at 90 to 100 ° C. for 40 minutes. The silver mirror film layer formation sample of Example 6 was obtained.
［実験例７］
（下塗り塗膜）
実験例３と同様にして、下塗り塗膜が形成された天然ゴムシートを得た。
[Experimental Example 7]
(Undercoat)
In the same manner as in Experimental Example 3, a natural rubber sheet on which an undercoat coating film was formed was obtained.
（銀鏡膜層）
銀鏡膜層は、実験例４の場合と同様にして調製した酸化銀錯体溶液に、実験例６で調製した表面がウレタン化されたコロイダルシリカを銀の固形分に対して、不揮発分質量比で６％添加混合し、透明な銀錯体／表面がウレタン化されたコロイダルシリカ複合液を得た。この銀錯体／表面がウレタン化されたコロイダルシリカ複合液を２−プロパノールで３倍に希釈して、下塗り塗膜が形成された天然ゴムシートの表面にスプレー塗装し、８０〜９０℃で３０分間乾燥して銀鏡膜層を形成させた。
(Silver mirror film layer)
In the silver mirror film layer, the colloidal silica whose surface was urethanized prepared in Experimental Example 6 was added to the silver oxide complex solution prepared in the same manner as in Experimental Example 4 in a non-volatile mass ratio with respect to the solid content of silver. 6% of the mixture was added and mixed to obtain a transparent silver complex / colloidal silica composite liquid having a urethane surface. This silver complex / colloidal silica composite liquid whose surface is urethanized is diluted 3-fold with 2-propanol and spray-coated on the surface of a natural rubber sheet on which an undercoat film has been formed, at 80 to 90 ° C. for 30 minutes. A silver mirror film layer was formed by drying.
（上塗り塗膜）
実験例３の下塗り塗料をそのまま上塗り塗料として使用してスプレー塗装後、９０〜１００℃で４０分間乾燥し、天然ゴムシートの表面に下塗り塗膜、銀鏡膜層及び上塗り塗膜が形成された実験例７の銀鏡膜層形成試料を得た。
(Top coat)
Experimental Example 3 An experiment in which an undercoat paint, a silver mirror film layer, and a top coat film were formed on the surface of a natural rubber sheet after spray coating using the undercoat paint as it is as an overcoat paint and then drying at 90 to 100 ° C. for 40 minutes. A silver mirror film layer-forming sample of Example 7 was obtained.
［比較例］
（下塗り塗膜）
アクリルポリオール樹脂（コータックスＬＨ６０１）８０質量部に酢酸ブチル２０質量部を加えて撹拌しながら均一に混合した。さらに、触媒としてジラウリル酸−ジ−ｎ−ブチルスズを０．０１質量部、レベラー（ＢＹＫ３００）を０．２質量部添加混合して、下塗り塗料の主剤を調製した。次いで、アダクトタイプのポリイソシアネート硬化剤（コロネートＨＬ）を、主剤：硬化剤＝１００：１０（質量比）の割合で混合し、シンナーで希釈し、黒色の天然ゴムシートにスプレー塗装した。次いで、９０〜１００℃で４０分間強制乾燥して下塗り塗料が形成された天然ゴムシートを得た。この比較例の下塗り塗膜は、実験例１の下塗り塗膜と比すると反応性軟化剤が配合されていないため、硬質膜となっている。
[Comparative example]
(Undercoat)
20 parts by mass of butyl acetate was added to 80 parts by mass of an acrylic polyol resin (Cotax LH601) and mixed uniformly with stirring. Further, 0.01 parts by weight of dilauric acid-di-n-butyltin and 0.2 parts by weight of leveler (BYK300) were added and mixed as a catalyst to prepare a base material for an undercoat paint. Next, an adduct type polyisocyanate curing agent (Coronate HL) was mixed at a ratio of main agent: curing agent = 100: 10 (mass ratio), diluted with thinner, and spray-coated on a black natural rubber sheet. Subsequently, it forcedly dried at 90-100 degreeC for 40 minutes, and obtained the natural rubber sheet in which the primer coating was formed. The undercoat film of this comparative example is a hard film because no reactive softener is blended as compared with the undercoat film of Experimental Example 1.
（銀鏡膜層）
銀鏡膜層は、実験例１の場合と同様にして形成した。
(Silver mirror film layer)
The silver mirror film layer was formed in the same manner as in Experimental Example 1.
（上塗り塗膜）
比較例の下塗り塗料をそのまま上塗り塗料として使用してスプレー塗装後、９０〜１００℃で４０分間乾燥し、天然ゴムシートの表面に下塗り塗膜、銀鏡膜層及び上塗り塗膜が形成された比較例の銀鏡膜層形成試料を得た。
(Top coat)
A comparative example in which the undercoat paint, the silver mirror film layer and the top coat film were formed on the surface of the natural rubber sheet after spray coating using the base coat of the comparative example as it was, followed by spray coating at 90 to 100 ° C. for 40 minutes. A silver mirror film layer-forming sample was obtained.
［各種物性の測定］
上述のようにして作成された実験例１〜７及び比較例の銀鏡膜層形成試料について、以下に示したとおりの各種物性の測定に供した。
（１）外観表価、
（２）付着性評価試験、
（３）伸び率測定、
（４）耐屈曲性試験、
（５）耐寒屈曲性試験、
（６）冷熱繰り返し付着性試験、
（７）耐湿付着性試験、
（８）耐熱性試験
（９）耐溶剤性試験、
（１０）耐酸性試験、及び、耐人工汗試験を行なった。
（１１）耐アルカリ性試験。
なお、それぞれの試験の具体的な測定方法及び判断基準は以下に示したとおりであり、結果は纏めて表１に示した。
[Measurement of various physical properties]
About the silver mirror film layer formation sample of Experimental Examples 1-7 and the comparative example produced as mentioned above, it used for the measurement of various physical properties as shown below.
(1) Appearance price,
(2) Adhesion evaluation test,
(3) Elongation measurement,
(4) Bending resistance test,
(5) Cold bending resistance test,
(6) Cold and hot repeated adhesion test,
(7) Moisture resistance test,
(8) Heat resistance test (9) Solvent resistance test,
(10) An acid resistance test and an artificial sweat test were performed.
(11) Alkali resistance test.
The specific measurement methods and judgment criteria for each test are as shown below, and the results are summarized in Table 1.
（１）鏡面外観評価：
上塗り塗面が形成された銀鏡膜層に、発色不良、クレーター、クラック膨れ、白亜化が目視できた場合は、×とし、目視できない場合は○とした。
(1) Mirror surface appearance evaluation:
In the silver mirror film layer on which the top coat surface was formed, when coloring failure, crater, crack blistering, and chalking could be visually observed, it was rated as x.
（２）付着性評価試験：
ＪＩＳ５６００−５−６（２００７）に準じて評価した。塗膜にカッターナイフを垂直に当てて、２ｍｍ×２ｍｍ角の碁盤目（１００マス）に切り込みを入れた後、接着強度０．４４±０．０５ｋｇｆ／ｍｍの接着テープを貼り付け、これを４５度の角度で引き剥がす付着試験を行った。結果は、塗膜の剥離が認められなかったものを○、剥離がみとめられたものを×とした。
(2) Adhesion evaluation test:
Evaluation was performed according to JIS 5600-5-6 (2007). After applying a cutter knife vertically to the coating film and making a cut in a grid of 2 mm × 2 mm square (100 squares), an adhesive tape with an adhesive strength of 0.44 ± 0.05 kgf / mm was applied. The adhesion test which peels at the angle of a degree was done. As a result, the case where peeling of the coating film was not recognized was evaluated as “◯”, and the case where peeling was observed was evaluated as “X”.
（３）伸び率：
ＪＩＳＫ７３１１に準拠。精密万能試験機（オートグラフＡＧ−１００ＫＮＧ、（株）島津製作所製）を用いて、約１００μｍの下塗り塗膜に対して焦点間距離２０ｍｍ、引張速度５０ｍｍ／ｍｉｎの条件で行った。
(3) Elongation rate:
Conforms to JISK7311. Using a precision universal testing machine (Autograph AG-100KNG, manufactured by Shimadzu Corporation), an undercoating film of about 100 μm was subjected to the conditions of a focal distance of 20 mm and a tensile speed of 50 mm / min.
（４）耐屈曲性の測定：
２３℃、１０ｍｍφの丸棒で下記（ｉ）及び(ii）に示した回数、折り曲げる試験を行い、その後に付着性試験を行った。
（ｉ）繰り返し曲げ１０回
（ii）繰り返し曲げ５０回
(4) Measurement of bending resistance:
A bending test was performed with a round bar of 23 ° C. and 10 mmφ for the number of times shown in (i) and (ii) below, followed by an adhesion test.
(I) Repeated bending 10 times (ii) Repeated bending 50 times
（５）耐寒屈曲性の測定：
−３０℃で５時間放置後、１０ｍｍφの丸棒で下記（ｉ）及び(ii）に示した回数、折り曲げる試験を行い、その後に付着性試験を行った。
（ｉ）繰り返し曲げ１０回
（ii）繰り返し曲げ５０回
(5) Measurement of cold bending resistance:
After leaving at −30 ° C. for 5 hours, a 10 mmφ round bar was subjected to a bending test as shown in (i) and (ii) below, followed by an adhesion test.
(I) Repeated bending 10 times (ii) Repeated bending 50 times
（６）冷熱繰り返し付着性試験：
−３０℃で２時間放置し、その後６０℃に２時間放置するというサイクルを３回行った後、付着性評価試験を行った。
(6) Cold and hot repeated adhesion test:
The adhesion evaluation test was conducted after three cycles of leaving at −30 ° C. for 2 hours and then leaving at 60 ° C. for 2 hours.
（７）耐湿付着性試験：
４０℃±１℃、相対湿度９５％以上の恒温槽内に収容して１００時間放置した後、付着性試験を行った。
(7) Moisture resistance test:
After being accommodated in a constant temperature bath at 40 ° C. ± 1 ° C. and a relative humidity of 95% or more and allowed to stand for 100 hours, an adhesion test was conducted.
（８）耐熱性：
８０℃±２℃の恒温槽内に２４時間放置した後、付着性評価試験を行った。
(8) Heat resistance:
After being left in a constant temperature bath at 80 ° C. ± 2 ° C. for 24 hours, an adhesion evaluation test was performed.
（９）耐溶剤性：
石油ベンジンを含んだ綿布に荷重１００ｇ／ｃｍ２を印加して１０往復させて塗膜の表面をこすり、塗膜の表面状態を評価した。異常がないものを○、傷つきがあるものを×とした。
(9) Solvent resistance:
A load of 100 g / cm 2 was applied to a cotton cloth containing petroleum benzine, and the coating film was rubbed 10 times to evaluate the surface condition of the coating film. The case where there was no abnormality was rated as ○, and the case where there was a scratch was rated as ×.
（１０）耐酸性：
０．１Ｎ硫酸水溶液０．２ｍｌを塗装表面に滴下し、２３℃、２時間放置後に外観を評価（スポットテスト法）した。
目視により観察し、塗膜の外観に異常やふくれが認められなかったものを○、認められたものを×とした。
(10) Acid resistance:
0.2 ml of a 0.1N sulfuric acid aqueous solution was dropped on the coating surface, and the appearance was evaluated after being allowed to stand at 23 ° C. for 2 hours (spot test method).
Observed by visual observation, those in which no abnormality or blistering was observed in the appearance of the coating film were marked with ◯, and those in which the abnormality was recognized were marked with ×.
（１１）耐アルカリ性：
０．１Ｎ苛性ソーダ水溶液０．２ｍｌを塗装表面に滴下し、２３℃、２時間放置後に外観を評価（スポットテスト法）した。
(11) Alkali resistance:
0.2 ml of 0.1N caustic soda aqueous solution was dropped on the coating surface, and the appearance was evaluated after being allowed to stand at 23 ° C. for 2 hours (spot test method).
［検 討］
表１に示した結果から、以下のことが分かる。
まず、実験例1と比較例の結果を検討する。
実験例1及び比較例で使用した下塗り塗料及び上塗り塗料（以下、両者を纏めて「塗料」ということがある）は、それぞれ主材としてアクリルポリオールを含み、硬化剤としてアダクトタイプのポリイソシアネートを含むものを用いてポリウレタン樹脂塗膜を形成している点では共通する。しかし、実験例１の塗料は主材としてさらに反応性軟化剤であるポリカプロラクトントリオールが添加されているのに対し、比較例の塗料ではこのような反応性軟化剤が添加されていない点で相違している。なお、アダプトタイプのポリイソシアネートは、ポリウレタン形成用の標準型硬化剤として汎用的に使用されているものである。なお、銀鏡膜層は両者ともに銀ナノ粒子分散液をスプレー塗装することにより形成しており、銀鏡膜層の形成方法に差異はない。
[Consideration]
From the results shown in Table 1, the following can be understood.
First, the results of Experimental Example 1 and Comparative Example are examined.
The undercoat and topcoat used in Experimental Example 1 and Comparative Example (hereinafter sometimes referred to as “paint”) include acrylic polyol as the main material and adduct-type polyisocyanate as the curing agent. It is common in the point which forms a polyurethane resin coating film using things. However, the coating material of Experimental Example 1 is different in that the reactive softening agent polycaprolactone triol is further added as a main material, whereas the reactive softening agent is not added to the comparative coating material. doing. In addition, the adapt type polyisocyanate is generally used as a standard curing agent for forming polyurethane. In addition, both silver mirror film layers are formed by spray-coating silver nanoparticle dispersion liquid, and there is no difference in the formation method of a silver mirror film layer.
これにより、比較例１では硬質のポリウレタン樹脂塗膜が得られ、このポリウレタン樹脂塗膜の伸び率は７％と非常に小さくなっている。それに対し、実験例１では、塗料の主材として反応性軟化剤であるポリカプロラクトントリオールが配合されているものを用いているため、軟質のポリウレタン樹脂塗膜が得られ、このポリウレタン樹脂塗膜の伸び率は１９８と、比較例のものに比すると非常に大きくなっている。また、両者とも鏡面外観は良好な結果が得られているが、実験例１の銀鏡膜層形成試料では耐寒屈曲性（ii）以外は全て良好な結果が得られているのに対し、比較例１の銀鏡膜層形成試料では、耐寒屈曲性（ii）だけでなく、耐屈曲性（ｉ）及び（ii）、耐寒屈曲性（ｉ）、冷熱繰り返し付着性試験も劣る結果となっている。なお、耐寒屈曲性（ii）は耐寒屈曲性（ｉ）よりも屈曲回数が多い過酷な試験である。したがって、実験例１と比較例との結果の対比から、ポリウレタン樹脂塗膜からなる下塗り塗膜及び上塗り塗膜ともに軟質で伸び率が大きな塗膜とすることにより、ゴム弾性体表面に下塗り塗膜、銀鏡膜層及び上塗り塗膜が形成された銀鏡膜層形成試料の各種物性が良好となることが分かる。 Thereby, in the comparative example 1, the hard polyurethane resin coating film was obtained, and the elongation rate of this polyurethane resin coating film is as very small as 7%. On the other hand, in Experimental Example 1, since the main component of the paint is a compound containing polycaprolactone triol, which is a reactive softening agent, a soft polyurethane resin coating film is obtained. The elongation rate is 198, which is much larger than that of the comparative example. In both cases, the mirror surface appearance shows good results, but the silver mirror film layer-formed sample of Experimental Example 1 shows good results except for cold bending resistance (ii), whereas the comparative example In the silver mirror film layer-formed sample, not only the cold bending resistance (ii), but also the bending resistance (i) and (ii), the cold bending resistance (i), and the cold repeated adhesion test were inferior. The cold bending resistance (ii) is a harsh test in which the number of bendings is larger than the cold bending resistance (i). Therefore, from the comparison of the results of Experimental Example 1 and Comparative Example, both the undercoating film and the topcoating film made of a polyurethane resin coating film are soft and have a large elongation rate. It can be seen that various physical properties of the silver mirror film layer-formed sample on which the silver mirror film layer and the top coat film are formed are good.
次に、実験例１〜実験例３の結果を検討する。
実験例１〜実験例３で使用した塗料は、それぞれ主材としてアクリルポリオールを含むものを用いている点では共通している。しかし、実験例１及び実験例３の塗料は主材中にさらに反応性軟化剤としてのポリカプロラクトントリオールが添加されており、また、実験例２の塗料の主材にはこのような反応性軟化剤が添加されておらず、さらに実験例１の塗料では硬化剤として標準型硬化剤であるアダプトタイプのポリイソシアネートを使用しているのに対し、実験例２及び実験例３の塗料では硬化剤として弾性型ポリイソシアネートを使用している点で相違している。なお、弾性ポリイソシアネートとは、ポリイソシアネートとポリアルキレングリコールエーテルとのウレタン化反応により得られたポリイソシアネート組成物である。
Next, the results of Experimental Examples 1 to 3 will be examined.
The coating materials used in Experimental Examples 1 to 3 are common in that the materials containing acrylic polyol are used as the main materials. However, the paints of Experimental Example 1 and Experimental Example 3 are further added with polycaprolactone triol as a reactive softener in the main material, and the reactive softening is applied to the main material of the paint of Experimental Example 2. In addition, the coating material of Experimental Example 1 uses the adapter type polyisocyanate that is a standard curing agent as the curing agent, whereas the coating materials of Experimental Example 2 and Experimental Example 3 use the curing agent. Is different in that an elastic polyisocyanate is used. The elastic polyisocyanate is a polyisocyanate composition obtained by a urethanization reaction between a polyisocyanate and a polyalkylene glycol ether.
すなわち、実験例１の塗料は主材によってポリウレタン樹脂塗膜に柔軟性を与えるようにしているのに対し、実験例２の塗料は硬化剤によってポリウレタン樹脂塗膜に柔軟性を与えるようにしており、さらに、実験例３の塗料は主材及び硬化剤の両者によってポリウレタン樹脂塗膜に柔軟性を与えるようにしている。なお、銀鏡膜層は両者ともに銀ナノ粒子分散液をスプレー塗装することにより形成しており、銀鏡膜層の形成方法に差異はない。 That is, while the paint of Experimental Example 1 gives flexibility to the polyurethane resin coating film by the main material, the paint of Experimental Example 2 gives flexibility to the polyurethane resin coating film by the curing agent. Furthermore, the coating material of Experimental Example 3 gives flexibility to the polyurethane resin coating film by both the main material and the curing agent. In addition, both silver mirror film layers are formed by spray-coating silver nanoparticle dispersion liquid, and there is no difference in the formation method of a silver mirror film layer.
これにより、実験例１では伸び率が１９８％のポリウレタン樹脂塗膜が得られ、実験例２では伸び率が２８３％のポリウレタン樹脂塗膜が得られ、実験例３では伸び率が４６３％と非常に大きなポリウレタン樹脂塗膜が得られている。そして、実験例１〜実験例３の銀鏡膜層形成試料は、いずれも耐寒屈曲性（ii）以外は全て良好な結果が得られている。以上の結果からすると、ポリウレタン樹脂塗膜の柔軟性を主材の組成によって付与しても、硬化剤の組成によって付与しても、伸び率が大きい限り、ゴム弾性体表面に下塗り塗膜、銀鏡膜層及び上塗り塗膜が形成された銀鏡膜層形成試料の各種物性が良好となることが分かる。 As a result, a polyurethane resin coating film having an elongation of 198% was obtained in Experimental Example 1, a polyurethane resin coating film having an elongation of 283% was obtained in Experimental Example 2, and an elongation of 463% was obtained in Experimental Example 3. A large polyurethane resin coating film is obtained. The silver mirror film layer-formed samples of Experimental Examples 1 to 3 are all good except for cold bending resistance (ii). Based on the above results, the flexibility of the polyurethane resin coating film is imparted by the composition of the main material or by the composition of the curing agent. It turns out that the various physical properties of the silver mirror film layer formation sample in which the film layer and the top coat film are formed are good.
次に、実験例４の結果を検討する。
実験例４は、素材としてブチルゴムシートを使用し、塗料の主材としてポリカーボネートポリオールと反応性軟化剤としてのポリカプロラクトントリオールを含むものを用い、硬化剤としてビウレット型ポリイソシアネートを含むものを用いてポリウレタン樹脂塗膜を形成しているものである。ブチルゴムは天然ゴムよりも硬質のゴム弾性体として知られているものであり、ポリカーボネートポリオールを含むポリウレタン塗料は、良好な特性を備えた高耐久の塗膜が得られることが知られているものである。また、ビウレット型ポリイソシアネートは、ポリカーボネートポリオールを用いたポリウレタン形成用の標準型硬化剤として汎用的に使用されているものである。なお、ここでは銀鏡膜形成方法として酸化銀錯体溶液をスプレー塗装することにより形成している。
Next, the result of Experimental Example 4 will be examined.
Experimental Example 4 uses a butyl rubber sheet as a raw material, a material containing polycarbonate polyol and polycaprolactone triol as a reactive softener as a main material of a paint, and a material containing biuret type polyisocyanate as a curing agent. A resin coating film is formed. Butyl rubber is known as a rubber elastic body harder than natural rubber, and polyurethane paint containing polycarbonate polyol is known to provide a highly durable coating film with good characteristics. is there. In addition, biuret type polyisocyanate is generally used as a standard curing agent for forming polyurethane using polycarbonate polyol. Here, as a silver mirror film forming method, the silver oxide complex solution is formed by spray coating.
これにより、得られたポリウレタン樹脂塗膜は、伸び率が８９％と、実験例１のものよりは小さく、比較例のものよりは大きくなっている。この銀鏡膜層形成試料によれば、耐屈曲性（ii）及び耐寒屈曲性（ii）以外は全て良好な結果が得られている。このことは、実験例４の銀鏡膜層形成試料は、塗膜の伸び率が実験例１のものよりも小さくなったことから、耐寒屈曲性（ii）だけでなく、耐屈曲性（ii）も劣る結果となったものと考えられる。なお、耐屈曲性（ii）も耐屈曲性（ｉ）よりも屈曲回数が大きい過酷な試験である。 Thereby, the obtained polyurethane resin coating film has an elongation of 89%, which is smaller than that of Experimental Example 1 and larger than that of Comparative Example. According to this silver mirror film layer-formed sample, good results were obtained except for the bending resistance (ii) and the cold bending resistance (ii). This is because, in the sample for forming a silver mirror film layer of Experimental Example 4, the elongation percentage of the coating film was smaller than that of Experimental Example 1, so that not only cold bending resistance (ii) but also bending resistance (ii) It is thought that the result was inferior. Note that the bending resistance (ii) is also a severe test in which the number of bendings is larger than the bending resistance (i).
次に、実験例５の結果を検討する。
実験例５は、素材としてエチレンプロピレンゴム（ＥＰＤＭ）シートを使用し、塗料の主材としてポリカーボネートポリオールと反応性軟化剤としてのポリカプロラクトントリオールを含むものを用い、硬化剤として弾性型ポリイソシアネートを含むものを用いてポリウレタン樹脂塗膜を形成しているものである。ＥＰＤＭゴムは、難接着性であるため、表面に変性ポリオレフィン系の接着用プライマーを塗装し、その表面に下塗り塗料を形成している。ここで用いている塗料は実験例３の塗料と同一のものであり、得られたポリウレタン樹脂塗膜の伸び率も実験例３の場合と同じ４６３％と非常に大きくなっている。また、ここでは銀鏡膜形成方法として酸化銀錯体溶液をスプレー塗装することにより形成している。
Next, the result of Experimental Example 5 will be examined.
Experimental Example 5 uses an ethylene propylene rubber (EPDM) sheet as a raw material, uses a polycarbonate polyol and polycaprolactone triol as a reactive softener as a main material of a paint, and includes an elastic polyisocyanate as a curing agent. A polyurethane resin coating film is formed using a material. Since EPDM rubber is difficult to adhere, a modified polyolefin-based adhesion primer is applied to the surface, and an undercoat paint is formed on the surface. The paint used here is the same as the paint of Experimental Example 3, and the elongation percentage of the obtained polyurethane resin coating film is as large as 463% as in the case of Experimental Example 3. Here, as a silver mirror film forming method, the silver oxide complex solution is formed by spray coating.
この銀鏡膜層形成試料によれば、耐寒屈曲性（ii）以外は全て良好な結果が得られており、実質的に実験例３の銀鏡膜層形成試料と同様の結果が得られている。このことは、素材としてのゴム弾性体の種類によらず、素材と下塗り塗料との間に良好な接着性が維持されていれば、ゴム弾性体表面に下塗り塗膜、銀鏡膜層及上塗り塗膜が形成された銀鏡膜層形成試料の各種物性が良好となることが分かる。 According to this silver mirror film layer-formed sample, good results were obtained except for cold bending resistance (ii), and substantially the same results as the silver mirror film layer-formed sample of Experimental Example 3 were obtained. This means that, regardless of the type of rubber elastic body as the material, if a good adhesion is maintained between the material and the undercoat paint, the surface of the rubber elastic body is coated with an undercoating film, a silver mirror film layer and an overcoating film. It can be seen that the various physical properties of the silver mirror film layer-formed sample on which the film is formed are good.
次に、実験例６及び実験例７の結果を検討する。
実験例１〜５で得られた銀鏡膜層形成試料では耐寒屈曲性（ii）の測定結果が劣ることが分かったが、この原因として銀鏡膜層と下塗り塗膜ないし上塗り塗膜との間の密着性が良好でないことに起因するものと考えられる。そこで、実験例６及び実験例７では、銀鏡膜層形成用溶液中に有機溶媒分散コロイダルシリカを用いて調製したウレタン化コロイダルシリカを添加したものを用いた。この銀鏡膜層形成用溶液としては、実験例６では上記特許文献３に記載の方法に基づく銀ナノ粒子分散液が、実験例７では上記特許文献１に記載の方法に基づく酸化銀錯体溶液が、それぞれ用いられている。その他の塗膜の形成方法は実験例３のものと同様である。
Next, the results of Experimental Example 6 and Experimental Example 7 will be examined.
It was found that the measurement results of cold bending resistance (ii) were inferior in the silver mirror film layer-formed samples obtained in Experimental Examples 1 to 5, but this was caused by the difference between the silver mirror film layer and the undercoat film or the topcoat film. This is considered to be caused by poor adhesion. Therefore, in Experimental Example 6 and Experimental Example 7, a solution in which urethanized colloidal silica prepared using organic solvent-dispersed colloidal silica was added to a silver mirror film layer forming solution was used. As the silver mirror film layer forming solution, a silver nanoparticle dispersion based on the method described in Patent Document 3 is used in Experimental Example 6, and a silver oxide complex solution based on the method described in Patent Document 1 is used in Experimental Example 7. Are used respectively. Other coating film forming methods are the same as those in Experimental Example 3.
実験例６及び実験例７で得られた銀鏡膜層形成試料では、それぞれのポリウレタン樹脂塗膜の伸び率は実験例３のものと同じ４６３％であるが、耐寒屈曲性（ii）の測定結果も含め、全て良好な測定結果が得られていることが分かる。この測定結果は、銀鏡膜層形成用溶液中にウレタン化コロイダルシリカが添加されているため、下塗り塗膜及び上塗り塗膜がともにポリウレタン樹脂塗膜であることと相まって、銀鏡膜層と下塗り塗層との間及び銀鏡膜層と上塗り塗膜との間の密着性がそれぞれ向上したため、及び、銀粒子間の緩衝作用によって銀鏡膜層の変形追従性が改善されたためと考えられる。 In the silver mirror film layer-formed samples obtained in Experimental Example 6 and Experimental Example 7, the elongation percentage of each polyurethane resin coating film is 463%, which is the same as that of Experimental Example 3, but the measurement result of cold bending resistance (ii) It can be seen that good measurement results are obtained. This measurement result shows that since the urethanized colloidal silica is added to the silver mirror film layer forming solution, both the undercoat film and the topcoat film are polyurethane resin films, It is considered that the adhesion between the silver mirror film layer and the top coat film was improved, and that the deformation followability of the silver mirror film layer was improved by the buffering action between the silver particles.
そのため、実験例６及び実験例７の測定結果は、実験例１〜５で得られた銀鏡膜層形成試料の場合においても、銀鏡膜層形成用溶液中にウレタン化コロイダルシリカを添加することによって耐寒屈曲性（ii）も良好な結果が得られるようになることを示唆するものである。なお、実験例６及び実験例７の銀鏡膜層形成試料間の構成の差異は、銀鏡膜形成方法が異なるのみであるから、銀鏡膜形成方法の差異は各種物性の測定結果に影響を与えないことも分かる。 Therefore, the measurement results of Experimental Example 6 and Experimental Example 7 are obtained by adding urethanized colloidal silica to the silver mirror film layer forming solution even in the case of the silver mirror film layer forming samples obtained in Experimental Examples 1 to 5. Cold bending resistance (ii) also suggests that good results will be obtained. In addition, since the difference in structure between the silver mirror film layer formation samples of Experimental Example 6 and Experimental Example 7 is only the silver mirror film forming method, the difference in the silver mirror film forming method does not affect the measurement results of various physical properties. I understand that.
なお、ウレタン化コロイダルシリカ調製の際には、弾性ポリイソシアネートを有機溶媒分散コロイダルシリカ１００質量部に対して３〜１２質量部の割合となるように添加することが好ましい。弾性ポリイソシアネートの添加割合が３質量％以下では、弾性ポリイソシアネート添加の効果が小さく、また、１２質量％以上の添加では得られたウレタン化コロイダルシリカ液（ウレタン化シリカゾル液）の保存性が低下する。 In preparing the urethanized colloidal silica, it is preferable to add the elastic polyisocyanate so as to have a ratio of 3 to 12 parts by mass with respect to 100 parts by mass of the organic solvent-dispersed colloidal silica. If the addition ratio of the elastic polyisocyanate is 3% by mass or less, the effect of the addition of the elastic polyisocyanate is small, and if the addition is 12% by mass or more, the storage stability of the urethanized colloidal silica liquid (urethanized silica sol liquid) is lowered. To do.
ここで、実験例１〜７及び比較例１の測定結果から、最適な塗膜（下塗り塗膜及び上塗り塗膜）の伸び率について検討する。
塗膜の伸び率は、実験例４及び比較例の結果から、８０％以上であれば、耐屈曲性（ii)及び耐寒屈曲性(ii)の測定結果を除いて、良好な結果が得られると考えられる。ただ、実験例４の塗膜の伸び率よりも大きい実験例１では、耐寒屈曲性(ii)の測定結果は実験例４の場合と変わらないが、耐屈曲性(ｉ)の測定結果が良好なものとなっていることから、塗膜の伸び率が１００％以上であれば耐屈曲性（ii)も良好な結果が得られると考えられる。なお、塗膜の伸び率が６００％を越える場合は、塗膜の傷つき性や鏡面外観が低下するため、８０％以上６００％以下が好ましく、１００％以上５００％以下がより好ましいことが分かる。
Here, from the measurement results of Experimental Examples 1 to 7 and Comparative Example 1, the elongation rate of the optimum coating film (undercoat film and topcoat film) is examined.
If the elongation percentage of the coating film is 80% or more from the results of Experimental Example 4 and Comparative Example, good results can be obtained except for the measurement results of bending resistance (ii) and cold bending resistance (ii). it is conceivable that. However, in Experimental Example 1, which is larger than the elongation percentage of the coating film of Experimental Example 4, the measurement result of cold bending resistance (ii) is not different from that of Experimental Example 4, but the measurement result of bending resistance (i) is good. Therefore, if the elongation percentage of the coating film is 100% or more, it is considered that good results in bending resistance (ii) can be obtained. In addition, when the elongation rate of a coating film exceeds 600%, since the damage property and mirror surface appearance of a coating film fall, it turns out that 80% or more and 600% or less are preferable, and 100% or more and 500% or less are more preferable.
また、実験例１〜７及び比較例１の測定結果から、塗膜の伸び率は、主材中の反応性軟化剤の含有割合によって変化させることができ、また、主材と弾性型ポリイソシアネートの混合比を変えることによっても変化させることができることが分かる。主材中に含有させる反応性軟化剤の割合は、主材１００質量部に対して５〜１０質量部とすることが好ましい。主材中に含有させる反応性軟化剤の割合が５質量部未満であると伸び率を所望の範囲内に維持することが困難になり、同じく１０質量部を越えると塗膜形成用の主要成分であるポリオール成分の含有割合が少なくなるので塗膜の強度が低下する。 Moreover, from the measurement results of Experimental Examples 1 to 7 and Comparative Example 1, the elongation percentage of the coating film can be changed depending on the content ratio of the reactive softener in the main material, and the main material and the elastic polyisocyanate. It can be seen that it can also be changed by changing the mixing ratio. The ratio of the reactive softener contained in the main material is preferably 5 to 10 parts by mass with respect to 100 parts by mass of the main material. When the proportion of the reactive softener contained in the main material is less than 5 parts by mass, it becomes difficult to maintain the elongation within a desired range. Since the content ratio of the polyol component is less, the strength of the coating film is lowered.
１０：銀鏡膜層が形成されたゴム弾性体
１１：ゴム弾性体
１２：下塗り塗膜
１３：銀鏡膜層
１４：上塗り塗膜
10: Rubber elastic body on which a silver mirror film layer is formed 11: Rubber elastic body 12: Undercoat film 13: Silver mirror film layer 14: Top coat film
本発明の第１の態様の銀鏡膜層が形成されたゴム弾性体は、ゴム弾性体の表面に形成された下塗り塗膜、前記下塗り塗膜の表面に形成された銀鏡膜層、及び、前記銀鏡膜層の表面に形成された上塗り塗膜、を有する銀鏡膜層が形成されたゴム弾性体であって、前記銀鏡膜層中には弾性型ポリイソシアネートで表面がウレタン化されたコロイダルシリカが含有されており、前記下塗り塗膜及び前記上塗り塗膜は、ポリオール成分を含む主材とポリイソシアネート成分を含む硬化剤とで形成された、それぞれの伸び率が８０％以上６００％以下である弾性ポリウレタン樹脂塗膜からなることを特徴とする。
The rubber elastic body in which the silver mirror film layer of the first aspect of the present invention is formed is an undercoat film formed on the surface of the rubber elastic body, a silver mirror film layer formed on the surface of the undercoat film, and the above A rubber elastic body having a silver mirror film layer having a top coat film formed on the surface of the silver mirror film layer, wherein the silver mirror film layer contains colloidal silica whose surface is urethanized with an elastic polyisocyanate. The undercoating film and the top coating film are formed of a main material containing a polyol component and a curing agent containing a polyisocyanate component, and each elongation is 80% or more and 600% or less. It consists of a polyurethane resin coating film.
係る態様の銀鏡膜層が形成されたゴム弾性体によれば、下塗り塗膜及び上塗り塗膜の伸び率が良好であり、しかも銀鏡膜層中に弾性型ポリイソシアネートで表面がウレタン化されたコロイダルシリカが含有されているため、銀鏡膜層もそれにつれて変形性が良好となるだけでなく、銀鏡膜層と下塗り塗膜との間及び銀鏡膜層と上塗り塗膜との間の密着性がそれぞれ向上し、また、銀粒子間の緩衝作用が良好になるので、銀鏡膜層の変形追従性が改善され、良好な物性を有する銀鏡膜層が形成される。これにより、鏡面外観、付着性、耐屈曲性、耐寒屈曲性、冷熱繰り返し性等に優れた銀鏡膜層が形成されたゴム弾性体が得られる。なお、本発明における伸び率は、ＪＩＳＫ７３１１に準拠する方法によって測定した数値を示す。また、塗膜の伸び率が８０％未満の場合は、基材の変形に対する塗膜の追随性が低下し、亀裂を生じたり、基材との間の密着性が低下するようになる。さらに、塗膜の伸び率が６００％を越える場合は、塗膜が柔らかすぎて傷付きやすくなるとともに耐薬品性も低下するため、特に上塗り塗料の溶剤アタックなどで鏡面外観が低下する。より好ましい下塗り塗膜及び上塗り塗膜の伸び率は、１００％以上５００％以下である。
According to the rubber elastic body in which the silver mirror film layer of this aspect is formed, the elongation rate of the undercoat film and the topcoat film is good, and the colloidal whose surface is urethanized with an elastic polyisocyanate in the silver mirror film layer since silica is contained, the silver mirror film layer also well that Do is good deformability as it, adhesion and between the silver mirror film layer and the top coat of the silver mirror film layer and the undercoating film is Since each improves and the buffering effect between silver particles becomes good, the deformation follow-up property of the silver mirror film layer is improved, and a silver mirror film layer having good physical properties is formed. As a result, a rubber elastic body on which a silver mirror film layer excellent in mirror surface appearance, adhesion, bending resistance, cold bending resistance, cold repeatability and the like is formed can be obtained. In addition, the elongation rate in this invention shows the numerical value measured by the method based on JISK7311. Moreover, when the elongation rate of a coating film is less than 80%, the followability of the coating film with respect to a deformation | transformation of a base material will fall, a crack will be produced, or adhesiveness between base materials will come to fall. Further, when the elongation percentage of the coating film exceeds 600%, the coating film is too soft and easily damaged, and the chemical resistance is also lowered, so that the mirror surface appearance is deteriorated particularly by a solvent attack of the top coating material. The elongation ratio of the more preferable undercoat film and topcoat film is 100% or more and 500% or less.
さらに、本発明の第６の態様のゴム弾性体の表面に銀鏡膜層を形成する方法は、
ゴム弾性体の表面に下塗り塗料を塗布して下塗り塗膜を形成する工程と、
前記下塗り塗膜の表面に銀鏡膜層形成用液を塗布して銀鏡膜層を形成する工程と、
前記銀鏡膜層の表面に上塗り塗料を塗布して上塗り塗膜を形成する工程と、
を備える、ゴム弾性体の表面に銀鏡膜層を形成する方法であって、
前記銀鏡膜層形成用液中に弾性型ポリイソシアネートで表面がウレタン化されたコロイダルシリカが含有されているものを用い、
前記下塗り塗料及び前記上塗り塗料として、それぞれポリオール成分を含む主材とポリイソシアネート成分を含む硬化剤とを含み、前記下塗り塗膜及び前記上塗り塗膜がそれぞれ伸び率８０％以上６００％以下の弾性ポリウレタン樹脂塗膜となるものを用いることを特徴とする。
Furthermore, the method for forming a silver mirror film layer on the surface of the rubber elastic body according to the sixth aspect of the present invention includes:
Applying an undercoat paint to the surface of the rubber elastic body to form an undercoat film;
Applying a silver mirror film layer forming solution to the surface of the undercoat coating film to form a silver mirror film layer;
Forming a top coat film by applying a top coat to the surface of the silver mirror film layer;
A method of forming a silver mirror film layer on the surface of a rubber elastic body,
Using the silver mirror film layer forming liquid containing colloidal silica whose surface is urethanized with an elastic polyisocyanate,
The undercoat paint and the top coat paint each include a main component containing a polyol component and a curing agent containing a polyisocyanate component, and the undercoat paint film and the top coat paint each have an elongation of 80% or more and 600% or less. A resin coating film is used.
また、本発明の第７の態様のゴム弾性体の表面に銀鏡膜層を形成する方法は、第６の態様のゴム弾性体の表面に銀鏡膜層を形成する方法において、前記下塗り塗料及び上塗り塗料として、前記主材中にポリカプロラクトンポリオールからなる反応性軟化剤を含むものを用いることを特徴とする。
The method for forming a silver mirror film layer on the surface of the rubber elastic body according to the seventh aspect of the present invention is the method for forming a silver mirror film layer on the surface of the rubber elastic body according to the sixth aspect. As the coating material, a material containing a reactive softener made of polycaprolactone polyol in the main material is used.
また、本発明の第８の態様のゴム弾性体の表面に銀鏡膜層を形成する方法は、第７の態様のゴム弾性体の表面に銀鏡膜層を形成する方法において、前記反応性軟化剤の含有割合が主材１００質量部に対して５〜１０質量部のものを用いることを特徴とする。
Moreover, the method for forming a silver mirror film layer on the surface of the rubber elastic body according to the eighth aspect of the present invention is the method for forming a silver mirror film layer on the surface of the rubber elastic body according to the seventh aspect, wherein the reactive softener The content ratio is 5 to 10 parts by mass with respect to 100 parts by mass of the main material.
また、本発明の第９の態様のゴム弾性体の表面に銀鏡膜層を形成する方法は、第６〜８のいずれかの態様のゴム弾性体の表面に銀鏡膜層を形成する方法において、前記硬化剤として弾性型ポリイソシアネートを含むものを用いることを特徴とする。
The method for forming a silver mirror film layer on the surface of the rubber elastic body according to the ninth aspect of the present invention is the method for forming a silver mirror film layer on the surface of the rubber elastic body according to any one of the sixth to eighth aspects. A material containing elastic polyisocyanate is used as the curing agent.
また、本発明の第１０の態様のゴム弾性体の表面に銀鏡膜層を形成する方法は、第６〜第９のいずれかの態様のゴム弾性体の表面に銀鏡膜層を形成する方法において、前記ゴム弾性体の表面に接着用プライマー層を形成し、前記接着用プライマー層の表面に前記下塗り塗料を塗布して下塗り塗層を形成することを特徴とする。
The method for forming a silver mirror film layer on the surface of the rubber elastic body according to the tenth aspect of the present invention is the method for forming a silver mirror film layer on the surface of the rubber elastic body according to any of the sixth to ninth aspects. A primer layer for adhesion is formed on the surface of the rubber elastic body, and the primer layer is formed by applying the primer coating on the surface of the primer layer for adhesion.
本発明の第６〜第１０の態様のゴム弾性体の表面に銀鏡膜層を形成する方法によれば、それぞれ本発明の第１〜第５の態様の銀鏡膜層が形成されたゴム弾性体を製造することができるようになる。
According to the method of forming the silver mirror film layer on the surface of the rubber elastic body of the sixth to tenth aspects of the present invention, the rubber elastic body on which the silver mirror film layer of the first to fifth aspects of the present invention is formed, respectively. Can be manufactured.
Claims (12)
前記下塗り塗膜の表面に形成された銀鏡膜層、及び、
前記銀鏡膜層の表面に形成された上塗り塗膜、
を有する銀鏡膜層が形成されたゴム弾性体であって、
前記下塗り塗膜及び前記上塗り塗膜は、ポリオール成分を含む主材とポリイソシアネート成分を含む硬化剤とで形成された、それぞれの伸び率が８０％以上６００％以下である弾性ポリウレタン樹脂塗膜からなることを特徴とする、銀鏡膜層が形成されたゴム弾性体。 Undercoat film formed on the surface of rubber elastic body,
A silver mirror film layer formed on the surface of the undercoat film, and
A top coat film formed on the surface of the silver mirror film layer,
A rubber elastic body in which a silver mirror film layer having
The undercoating film and the top coating film are formed from an elastic polyurethane resin coating film formed of a main material containing a polyol component and a curing agent containing a polyisocyanate component, each having an elongation of 80% or more and 600% or less. A rubber elastic body in which a silver mirror film layer is formed.
前記下塗り塗膜の表面に銀鏡膜層形成用液を塗布して銀鏡膜層を形成する工程と、
前記銀鏡膜層の表面に上塗り塗料を塗布して上塗り塗膜を形成する工程と、
を備える、ゴム弾性体の表面に銀鏡膜層を形成する方法であって、
前記下塗り塗料及び前記上塗り塗料として、それぞれポリオール成分を含む主材とポリイソシアネート成分を含む硬化剤とを含み、前記下塗り塗膜及び前記上塗り塗膜がそれぞれ伸び率８０％以上６００％以下の弾性ポリウレタン樹脂塗膜となるものを用いることを特徴とする、ゴム弾性体の表面に銀鏡膜層を形成する方法。 Applying an undercoat paint to the surface of the rubber elastic body to form an undercoat film;
Applying a silver mirror film layer forming solution to the surface of the undercoat coating film to form a silver mirror film layer;
Forming a top coat film by applying a top coat to the surface of the silver mirror film layer;
A method of forming a silver mirror film layer on the surface of a rubber elastic body,
The undercoat paint and the top coat paint each include a main component containing a polyol component and a curing agent containing a polyisocyanate component, and the undercoat paint film and the top coat paint each have an elongation of 80% or more and 600% or less. A method for forming a silver mirror film layer on the surface of a rubber elastic body, characterized by using a resin coating film.
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