JPS6153448B2 - - Google Patents
Info
- Publication number
- JPS6153448B2 JPS6153448B2 JP10962080A JP10962080A JPS6153448B2 JP S6153448 B2 JPS6153448 B2 JP S6153448B2 JP 10962080 A JP10962080 A JP 10962080A JP 10962080 A JP10962080 A JP 10962080A JP S6153448 B2 JPS6153448 B2 JP S6153448B2
- Authority
- JP
- Japan
- Prior art keywords
- gold
- silver
- ultraviolet curable
- curable resin
- coating
- 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.)
- Expired
Links
- 229920005989 resin Polymers 0.000 claims description 89
- 239000011347 resin Substances 0.000 claims description 89
- 229910052737 gold Inorganic materials 0.000 claims description 69
- 239000010931 gold Substances 0.000 claims description 69
- 241000218202 Coptis Species 0.000 claims description 68
- 244000062175 Fittonia argyroneura Species 0.000 claims description 68
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 68
- 239000010410 layer Substances 0.000 claims description 51
- 238000000576 coating method Methods 0.000 claims description 46
- 239000011248 coating agent Substances 0.000 claims description 45
- 239000003973 paint Substances 0.000 claims description 41
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 39
- 229910052709 silver Inorganic materials 0.000 claims description 39
- 239000004332 silver Substances 0.000 claims description 39
- 239000011247 coating layer Substances 0.000 claims description 37
- -1 methacryloyl group Chemical group 0.000 claims description 23
- 239000003085 diluting agent Substances 0.000 claims description 19
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 9
- 229920006254 polymer film Polymers 0.000 claims description 7
- 238000005987 sulfurization reaction Methods 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 239000002932 luster Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- 229910000846 In alloy Inorganic materials 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- YZASAXHKAQYPEH-UHFFFAOYSA-N indium silver Chemical compound [Ag].[In] YZASAXHKAQYPEH-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241001265525 Edgeworthia chrysantha Species 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001756 Polyvinyl chloride acetate Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000180 alkyd Polymers 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
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexyloxide Natural products O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- KJCLYACXIWMFCC-UHFFFAOYSA-M sodium;5-benzoyl-4-hydroxy-2-methoxybenzenesulfonate Chemical compound [Na+].C1=C(S([O-])(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 KJCLYACXIWMFCC-UHFFFAOYSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Laminated Bodies (AREA)
Description
本発明は新規な耐硫化性金銀糸に関する。
従来より高分子フイルムまたは目止剤を塗布し
た和紙などの可撓性支持体上に直接またはアンダ
ーコーテイング層を介して純銀の蒸着層を設けた
フイルム状物をスリツトしてなる金銀糸、前記フ
イルム状物を２枚貼合わせたものをスリツトして
なる金銀糸などが知られている。
しかしながら、前記金銀糸において、純銀の蒸
着層はコーテイング層、支持体などにより被覆さ
れているとはいえ、大気中の硫化水素ガスあるい
は硫化物などと反応して硫化銀を生じやすく、銀
光沢が失なわれ黄色ないし黒色に変化する。した
がつて従来の金銀糸は保存中にその商品価値が大
巾に低下するという欠点があつた。この欠点を解
消するため種々の対策が講じられてきたが、いず
れも不充分である。たとえば純銀以外の耐硫化性
金属、たとえばアルミニウム、銀―インジウム合
金などの蒸着層を用いることが行なわれている
が、純銀のもつ深みとやわらかみのある光沢は他
の金属では到底えられないものであり、しかも銀
―インジウム合金の蒸着層を用いるばあいは耐汗
性など他の性能が低下し、しかも高価であるなど
の欠点がある。
また前述の金銀糸におけるコーテイング層は一
般に焼付塗料により形成されているが、焼付時の
高温で銀蒸着層の表面が黄変しやすい、支持体が
いたみやすい、さらにえられるコーテイング層が
硬く風合がわるいなどの問題がある。しかも溶剤
型焼付塗料を用いるばあいには溶剤の揮散による
公害上の問題がある。
本発明は前記の点に鑑みて、純銀の蒸着層を用
いながら耐硫化性にすぐれ、しかもコーテイング
層の形成に焼付塗料を用いるばあいの種々の問題
を完全に排除した金銀糸を提供するものである。
すなわち本発明は、
(1) 可撓性支持体上に直接または紫外線硬化性樹
脂塗料の硬化塗膜であるアンダーコーテイング
層を介して銀蒸着層を設け、そのうえに紫外線
硬化性樹脂塗料の硬化塗膜であるトツプコーテ
イング層を設けてなるフイルム状物のスリツト
糸であつて、かつ前記紫外線硬化性樹脂塗料が
樹脂成分および反応性稀釈剤のいずれもがアク
リロイル基および（または）メタクリロイル基
を有するものであることを特徴とする耐硫化性
金銀糸（以下、金銀糸（）という）、
(2) 可撓性支持体上に直接または紫外線硬化性樹
脂塗料の硬化塗膜であるアンダーコーテイング
層を介して銀蒸着層を設け、そのうえに紫外線
硬化性樹脂塗料の硬化塗膜であるトツプコーテ
イング層を設けてなるフイルム状物を２枚該支
持体を内側にして接着剤で貼合わせたもののス
リツト糸であつて、かつ前記紫外線硬化性樹脂
塗料が樹脂成分および反応性稀釈剤のいずれも
がアクリロイル基および（または）メタクリロ
イル基を有するものであることを特徴とする耐
硫化性金銀糸（以下、金銀糸（）という）、
および
(3) 透明な可撓性支持体上に紫外線硬化性樹脂塗
料の硬化塗膜であるアンダーコーテイング層を
介して銀蒸着層を設けてなるフイルム状物を２
枚該銀蒸着層を内側にして接着剤で貼合わせた
もののスリツト糸であつて、かつ前記紫外線硬
化性樹脂塗料が樹脂成分および反応性稀釈剤の
いずれもがアクリロイル基および（または）メ
タクリロイル基を有するものであることを特徴
とする耐硫化性金銀糸（以下、金銀糸（）と
いう）に関する。
本発明はのちに詳述する紫外線硬化性樹脂塗料
で形成したコーテイング層が意外にも硫化水素ガ
スないし硫化物に対してきわめてすぐれた遮断作
用を示すという本発明者らの見出したまつたく新
たな知見に基づいて完成されたものである。
しかして本発明の金銀糸は従来の銀蒸着層を用
いる金銀糸におけるコーデイング層を紫外線硬化
性樹脂塗料で形成したことを特徴とするものであ
り、該コーテイング層が硫化水素ガスないし硫化
物に対してきわめてすぐれた遮断作用を示すため
銀蒸着層の硫化による変色が完全に防止され、耐
硫化性にすぐれたものである。
しかも銀蒸着層を用いているため他の耐硫化性
金属を用いるばあいの、光沢が劣る、耐硫化性以
外の他の性能が劣る、高価であるなどの欠点が排
除される。
さらに本発明に用いる紫外線硬化性樹脂塗料は
紫外線照射するだけでとくに加熱を要せず硬化
し、比較的柔軟な塗膜を与えるから、従来の焼付
塗料を用いるばあいにおけるごとき焼付時の高温
で銀蒸着層の表面が黄変する、支持体がいたみや
すい、コーテイング層が硬く風合がわるいなどの
問題が解決され、きわめて高品位の金銀糸がえら
れるという特徴がある。また本発明に用いる紫外
線硬化性樹脂塗料は無溶剤であるため公害上の観
点からもすぐれている。
本発明で用いる紫外線硬化性樹脂塗料とは、紫
外線の照射によりとくに加熱する必要もなく数秒
ないし数分間で容易に硬化して柔軟かつ強靫な塗
膜を形成しうる塗料である。該塗料は樹脂成分、
反応性稀釈剤および光重合開始剤を必須成分とし
て含有し、その他着色剤、非反応性樹脂などの各
種の添加剤を含有しうるものである。
前記樹脂成分はその分子中に少なくとも１個の
付加重合性二重結合を有する重合体またはオリゴ
マーであり、常温で固体であつても液状であつて
もよい。液状の樹脂成分は反応性稀釈剤をも兼ね
ることができる。かかる重合体またはオリゴマー
としては不飽和ポリエステル系樹脂、アクリロイ
ル基反応型樹脂、アリル基反応型樹脂、ゾル型樹
脂、チオール／エン系樹脂などがあるが、銀蒸着
層との密着性、硫化水素ガスないし硫化物の遮断
性、耐薬品性、塗膜形成作業性などの観点からは
アクリロイル基反応型樹脂が最良の結果を与え、
本発明の目的に合致するものであることが見出さ
れた。このようなアクリロイル基反応型樹脂は、
アクリロイル基および（または）メタクリロイル
基を少なくとも１個、好ましくは２個以上その分
子中に有するものであつて、たとえば水酸基、イ
ソシアネート基、カルボキシル基、エポキシ基な
どを有する低分子量化合物や重合体にアクリロイ
ル基および（または）メタクリロイル基含有単量
体を反応させてえられるものであり、さらにかか
る樹脂を油、脂肪酸などで変性したものであつて
もよい。なお以下の記述において、アクリロイル
基、アクリレートまたはアクリルというときはメ
タクリロイル基、メタクリレートまたはメタクリ
ルを含む概念として用いる。前記アクリロイル基
反応型樹脂の具体例としては、たとえば単体ポリ
オールのアクリレート、側鎖アクリロイル基型ア
クリル樹脂プレポリマー、テロメル化ポリエステ
ルアクリレート、テロメル化ポリアミドアクリレ
ート、ウレタン樹脂のアクリレート、シリコーン
樹脂のアクリレートなどがあげられる。
前記反応性稀釈剤とは常温で液体の付加重合性
化合物であつて、前記樹脂成分を溶解したり、そ
の粘度を調節する作用を有するとともに前記樹脂
成分を架橋したりあるいはそれ自身で重合または
架橋したりして強靫な塗膜の形成を助ける作用を
有するものである。かかる反応性稀釈剤も多数知
られているが、とくにアクリル系稀釈剤が本発明
の目的に含致するものであることが見出された。
アクリル系稀釈剤の具体例としては、たとえばポ
リエチレングリコールジアクリレート、２―エチ
ルヘキシルアクリレート、テトラヒドロフルフリ
ルアクリレート、ヒドロキシプロピルアクリレー
ト、ジエチレングリコールエチルエーテルアクリ
レート、ジエチレングリコールジアクリレート、
ネオペンチルグリコールジアクリレート、ヒドロ
ピバリン酸ネオペンチルエステルジアクリレー
ト、トリメチロールプロパントリアクリレート、
１，６―ヘキサンジオールジアクリレート、ジベ
ンタエリスリトールヘキサアクリレート、アジピ
ン酸ネオペンチルエステルジアクリレート、テト
ラメチロールメタンテトラアクリレート、（ビス
フエノールＡ）ビスジエチレングリコールエーテ
ルジアクリレートなどがあげられる。
前記光重合開始剤とは紫外線照射によつて溶易
にフリーラジカルを発生する化合物であり、たと
えばベンゾイルアルキルエーテル類、α―アシロ
キシムエステル類、アセトフエノン類、ベンゾフ
エノン類、ベンジルケタール類、ケトン―アミン
類などの化合物が好ましく用いられる。
本発明に用いる紫外線硬化性樹脂塗料におい
て、樹脂成分に対する反応性稀釈剤の割合は、樹
脂成分100部（重量部、以下同様）に対して反応
性稀釈剤20〜150部の割合が好ましい。反応性稀
釈剤の割合が20部より少なくなると、一般的に塗
料の粘度が高くなりすぎて塗装適性がわるくな
り、またえられる塗膜が硬くなりすぎて可撓支持
体の変形、変質をもたらすことがある。一方150
部を超えると、塗料の硬化速度が低下して生産性
がわるくなるだけでなく、硫化水素ガスないし硫
化物の遮断性、耐薬品性などの塗膜性能が悪化
し、また銀蒸着層や可撓性支持体との密着性が低
下し、さらに未反応の反応性稀釈剤が塗膜中に残
ることがある。光重合開始剤は通常樹脂成分と反
応性稀釈剤の合計量100部に対して１〜８部程度
用いられる。
本発明においては前記のごとき組成の紫外線硬
化性樹脂塗料を用いることにより所期の目的が達
成されるが、さらに該塗料中につぎのごとき非反
応性樹脂を配合するときは塗膜のレベリング性が
より向上されて均一な厚さの塗膜がえられること
が見出された。かかる非反応性樹脂としては、た
とえばシクロヘキサノン系ケトン樹脂、ポリビニ
ルブチラール、セルロース誘導体、ポリアミド系
樹脂、環化ゴム、フエノール系樹脂、ポリエステ
ル系樹脂、酢酸ビニル系樹脂、アクリル系樹脂、
シリコーン系樹脂などがあげられる。非反応性樹
脂は通常樹脂成分100部に対して40部以下で用い
られる。非反応性樹脂が40部を超えると塗料の硬
化不良を生じて塗膜性能が低下する傾向がある。
本発明に用いる紫外線硬化性樹脂塗料には染
料、透明性有機顔料などの着色剤、紫外線吸収剤
などの添加剤を適宜配合してもよい。
つぎに本発明の金銀糸を金銀糸（），（）お
よび（）について順に説明する。
まず金銀糸（）について説明すると、用いる
可撓性支持体としては、たとえばポリエステル、
ポリアミド、ポリアミドイミド、ポリエチレン、
ポリプロピレン、ポリカーボネート、ポリ塩化ビ
ニル、セルロースアセテートなどのフイルムおよ
びセロハンなどの高分子フイルム、和紙などがあ
げられる。通常高分子フイルムとしては厚さが６
〜50μ程度のものが、和紙としては坪量が12〜25
ｇ／m2程度のものが用いられる。和紙支持体を用
いるばあいは目止剤を塗布しておく。目止剤とし
てはとくに制限されず通常の樹脂塗料が用いられ
るが、とくに前記紫外線硬化性樹脂塗料が好まし
い。目止剤の塗料量は３〜７ｇ／m2（固形分換
算、以下同様）程度である。
前記支持体上に直接または前記紫外線硬化性樹
脂塗料のアンダーコーテイング層を設けたのち銀
蒸着層を設け、そのうえに前記紫外線硬化性樹脂
塗料のトツプコーテイング層を形成する。
紫外線硬化性樹脂塗料によるトツプコーテイン
グ層およびアンダーコーテイング層の形成は該塗
料を塗布したのち紫外線を照射すればよく、とく
に加熱は要しない。トツプコーテイング層および
アンダーコーテイング層の厚さは通常0.5〜２μ
程度である。アンダーコーテイング層は耐硫化性
をより向上させたいばあい、高分子フイルム支持
体で銀蒸着層との密着性がよくないものを用いる
ばあい、透明な高分子フイルム支持体を用い該支
持体側にのみあるいは該支持体側およびトツプコ
ーテイング層側のいずれの側にも経時的に変色し
ない銀光沢を所望するばあいなどに設ける。支持
体側またはトツプコーテイング層側のいずれか一
方の側のみに銀光沢を所望するばあいは、トツプ
コーテイング層およびアンダーコーテイング層の
うちいずれか一方を不透明に着色してもよい。ま
た銀光沢以外の各種色彩の金属光沢を所望するば
あいはトツプコーテイング層および（または）ア
ンダーコーテイング層を透明に着色する。
銀蒸着層の形成は真空蒸着法、スパツタリング
法、イオンプレーテイング法などの通常の方法に
よつて行なわれ、その厚さは0.03〜0.15μ程度で
ある。
前記のごとくしてえられたフイルム状物をマイ
クロスリツターなどで適宜の巾、たとえば0.15〜
1.5mm程度にスリツトすることにより金銀糸
（）がえられる。この金銀糸はそのまま平金銀
糸として用いてもよく、あるいは他の糸、たとえ
ばレーヨン、絹、綿、テトロン、ナイロンなどの
糸と羽衣撚り、丸撚り、タスキ撚りして撚金銀糸
として用いてもよい。
金銀糸（）は前記金銀糸（）の製造に用い
たフイルム状物を２枚その支持体を内側にして接
着剤で貼合わせたものを金銀糸（）のばあいと
同様にスリツトすることによりえられる。接着剤
としては酢酸ビニル樹脂系、酢酸ビニル―エチレ
ン共重合樹脂系、ポリビニルアルコール、エポキ
シ樹脂系、ウレタン樹脂系、シリコーン系、ニト
リルゴム系などの接着剤が適宜用いられる。金銀
糸（）の２ブライ構成は支持体として和紙を用
いるばあいに好適に採用される。
金銀糸（）は、支持体として透明なものを用
い、これに紫外線硬化性樹脂塗料のアンダーコー
テイング層を設け、そのうえに銀蒸着層、さらに
要すれば紫外線硬化性樹脂塗料のトツプコーテイ
ング層を設けてなるフイルム状物を２枚該銀蒸着
層（またはトツプコーテイング層）を内側にして
接着剤で貼合わせたものを金銀糸（）のばあい
と同様にスリツトすることによりえられる。透明
な支持体としては前記の高分子フイルムが用いら
れる。アンダーコーテイング層、トツプコーテイ
ング層および銀蒸着層の形成などは金銀糸（）
のばあいと同様でよく、フイルム状物の貼合わせ
は金銀糸（）のばあいと同様に行なわれる。
本発明の金銀糸は耐硫化性がすぐれているた
め、従来の銀蒸着層を用いる金銀糸にかえて各種
製品に好適に用いられ、すぐれた銀光沢を恒久的
に維持しうる製品を与える。
つぎに実施例および比較例をあげて本発明の金
銀糸を説明する。
実施例 １
厚さ12μの長尺のポリエチレンテレフタレート
フイルムの片面につぎの組成の紫外線硬化性樹脂
塗料(A)をロールコーターで連続的に塗布し、フイ
ルムを約35m／分で移送しながら出力4kw
（80W／cm）の高圧水銀灯〔(株)オーク製作所製〕
を３本用いて95mW／cm2（365nm近辺における照
度）の強度で紫外線を照射して塗膜を硬化せしめ
て、厚さ１μのアンダーコーテイング層を形成し
た。
紫外線硬化性樹脂塗料(A)
〔粘度40±5cP（25℃）〕
成 分 部
エポキシアクリレート樹脂 40
（分子量1500、分子量1000あたり約３個のアク
リロイル基を有する）
ポリエチレングリコール―400ジアクリレート
23
ネオペンチルグリコールジアクリレート ５
アジピン酸ネオペンチルエステルジアクリレー
ト 10
２―ヒドロキシ―３―フエノキシプロピルアク
リレート 10
２―ヒドロキシプロピルアクリレート 10
ベンゾフエノン ５
ｐ―ジエトキシアセトフエノン ３
ハイラツク11（日立化成工業(株)製ケトン樹脂）
５
セルロースアセテートプチレート １
シリコーン 200（ppm）
前記アンダーコーテイング層上に真空蒸着法に
より連続的に銀を蒸着して厚さ0.08μの銀蒸着層
を形成し、そのうえに前記紫外線硬化性樹脂塗料
(A)にさらに酸化チタン22部を加えたもの〔以下、
紫外線硬化性樹脂塗料（A′）という〕を前記と
同様に連続的に塗布、硬化して厚さ１μのトツプ
コーテイング層を形成した。
えられたフイルム状物をマイクロスリツターで
0.38mmの巾にスリツトして金銀糸をえた。
実施例 ２
紫外線硬化性樹脂塗料(A)にかえてつぎの組成の
紫外線硬化性樹脂塗料(B)を用い、かつ紫外線硬化
性樹脂塗料（A′）にかえて紫外線硬化性樹脂塗
料(B)にさらに酸化チタン31部を加えたもの〔以
下、紫外線硬化性樹脂塗料（B′）という〕を用い
たほかは実施例１と同様にして金銀糸をえた。
紫外線硬化性樹脂塗料(B)
〔粘度45±5cP（25℃）〕
成 分 部
ウレタンアクリレート樹脂 45
（分子量1500、分子量1000あたり約２個のアク
リロイル基を有する）
ポリエチレングリコール―400ジアクリレート
28
ネオペンチルグリコールジアクリレート 10
テトラヒドロフルフリルアクリレート 20
ベンジルケタール ５
ポリビニルプチラール ３
セルロースアセテート １
シリコーン 200（ppm）
実施例 ３
トツプコーテイング層を紫外線硬化性樹脂塗料
(A)を用いて形成したほかは実施例１と同様にして
金銀糸をえた。
実施例 ４
アンダーコーテイング層を省略し、かつトツプ
コーテイング層を紫外線硬化性樹脂塗料(A)を用い
て形成したほかは実施例１と同様にして金銀糸を
えた。
実施例 ５
坪量18ｇ／m2のミツマタ混入和紙の片面に目止
剤として紫外線硬化性樹脂塗料(A)を塗布量６ｇ／
m2で塗布し、実施例１のばあいと同様にして硬化
した。
前記目止剤を塗布した和紙をポリエチレンテレ
フタレートフイルムにかえて用いかつトツプコー
テイング層を紫外線硬化性樹脂塗料(A)を用いて形
成したほかは実施例１と同様にしてフイルム状物
をえ、ついでこれを実施例１と同様にスリツトし
て金銀糸をえた。
実施例 ６
実施例５でえられたフイルム状物を２枚和紙を
内側にして酢酸ビニル樹脂系接着剤を用いて貼合
わせ、ついで実施例１と同様にスリツトして金銀
糸をえた。
実施例 ７
トツプコーテイング層を省略したほかは実施例
１と同様にしてフイルム状物をえ、これを２枚銀
蒸着層を内側にしてウレタン樹脂系接着剤を用い
て貼合わせ、ついで実施例１と同様にスリツトし
て金銀糸をえた。
前記実施例１〜７でえられた金銀糸は、支持体
に何らの変形、変質も認められず、かつ純銀に固
有のすぐれた銀光沢を呈し、しかも風合がすぐ
れ、きわめて高品位なものであつた。
比較例 １
アンダーコーテイング層およびトツプコーテイ
ング層をアミノアルキツド樹脂塗料を用い、180
℃で38秒間焼付して形成したほかは実施例１と同
様にして金銀糸をえた。
えられた金銀糸は、支持体に変形、変質が認め
られ、銀蒸着層に黄変が生じ銀光沢が損なわれ、
かつ風合の劣るものであつた。
前記実施例１〜７および比較例１でえられた金
銀糸について硫化水素テストを行なつた。硫化水
素テストは試料を温度20℃、95％RH、硫化水素
濃度0.6重量％の零囲気中に72時間放置すること
によつて行なつた。
テスト後金銀糸の光沢の変化を観察した。光沢
の判定はつぎの５段階評価によつて行なつた。
評価値
５ きわめて良好（純銀の光沢）
４ 良 好
３ やや良好
２ やや不良
１ 不 良
なお光沢の観察は実施例１〜２および比較例１
の金銀糸のばあいは支持体側、実施例４〜５の金
銀糸のばあいはトツプコーテイング層側について
行ない、実施例３および６〜７の金銀糸のばあい
は両側について行なつたが同一の評価値をえた。
結果を第１表に示す。
また第１表には、スリツトして金銀糸にする前
のフイルム状物について耐摩耗性および耐光性を
測定した結果および金銀糸の光沢、風合を調べた
結果も併せて示した。
前記耐摩耗性試験は学振型往復摩耗試験（上野
山機工(株)製）を用い、荷重200ｇ、30回往復
（分）の条件で行なつた。前記耐光性試験はJIS
Ｌ 0841に準じで行なつた。また風合の評価はつ
ぎの５段階評価によつて行なつた。
評価値
５ きわめて良好
４ 良 好
３ やや良好
２ やや不良
１ 不 良
比較例 ２
アンダーコーテイング層およびトツプコーテイ
ング層をアクリル樹脂塗料を用い、180℃で30秒
間焼付して形成したほかは実施例１と同様にして
金銀糸をえた。
比較例 ３
アンダーコーテイング層およびトツプコーテイ
ング層をウレタン樹脂塗料を用い、180℃で30秒
間焼付して形成したほかは実施例１と同様にして
金銀糸をえた。
比較例 ４
アンダーコーテイング層およびトツプコーテイ
ング層を尿素―メラミン樹脂塗料を用い、180℃
で30秒間焼付して形成したほかは実施例１と同様
にして金銀糸をえた。
比較例 ５
アンダーコーテイング層およびトツプコーテイ
ング層をエポキシ樹脂塗料を用い、180℃で30秒
間焼付して形成したほかは実施例１と同様にして
金銀糸をえた。
比較例 ６
アンダーコーテイング層およびトツプコーテイ
ング層をニトロセルロース樹脂塗料を用い、180
℃で30秒間乾燥して形成したほかは実施例１と同
様にして金銀糸をえた。
比較例２〜６でえられた金銀糸およびスリツト
する前のフイルム状物について前記と同様な試験
を行なつた。結果を第１表に示す。
The present invention relates to a novel sulfide-resistant gold and silver thread. Gold and silver threads made by slitting a film-like material in which a vapor-deposited layer of pure silver is provided directly or via an undercoating layer on a flexible support such as a polymer film or Japanese paper coated with a filler, and the above-mentioned film. Gold and silver threads are known, which are made by slitting two pieces of material pasted together. However, in the gold and silver threads, although the vapor-deposited layer of pure silver is covered with a coating layer, a support, etc., it easily reacts with hydrogen sulfide gas or sulfides in the atmosphere to form silver sulfide, and the silver luster is lost. It is lost and turns yellow or black. Therefore, conventional gold and silver threads had the disadvantage that their commercial value decreased significantly during storage. Various measures have been taken to overcome this drawback, but all of them are insufficient. For example, vapor-deposited layers of sulfide-resistant metals other than pure silver, such as aluminum and silver-indium alloys, have been used, but the depth and soft luster of pure silver cannot be achieved with other metals. Moreover, when a deposited layer of silver-indium alloy is used, other properties such as sweat resistance deteriorate, and there are also drawbacks such as high cost. In addition, the coating layer of the gold and silver threads mentioned above is generally formed with baking paint, but the surface of the silver vapor deposited layer tends to yellow due to the high temperature during baking, the support is easily damaged, and the resulting coating layer is hard and has a hard texture. There are problems such as being lazy. Moreover, when a solvent-based baking paint is used, there is a problem of pollution due to volatilization of the solvent. In view of the above points, the present invention provides a gold and silver thread that uses a vapor-deposited layer of pure silver, has excellent sulfidation resistance, and completely eliminates the various problems that occur when baking paint is used to form a coating layer. be. That is, the present invention provides: (1) a silver vapor deposited layer is provided on a flexible support directly or via an undercoating layer which is a cured coating of an ultraviolet curable resin coating; slit yarn of a film-like material provided with a top coating layer, and the ultraviolet curable resin coating has a resin component and a reactive diluent both having an acryloyl group and/or a methacryloyl group. Sulfide-resistant gold and silver threads (hereinafter referred to as gold and silver threads) characterized by It is a slit thread made by laminating two film-like materials with a silver vapor-deposited layer and a top coating layer, which is a cured coating film of an ultraviolet curable resin paint, with the support on the inside using an adhesive. , and the ultraviolet curable resin coating is characterized in that both the resin component and the reactive diluent have an acryloyl group and/or a methacryloyl group (hereinafter referred to as gold and silver thread). ),
and (3) a film-like material in which a silver vapor-deposited layer is provided on a transparent flexible support through an undercoating layer, which is a cured coating film of an ultraviolet curable resin paint.
It is a slit thread made of two sheets bonded together with an adhesive with the silver vapor deposited layer on the inside, and the ultraviolet curable resin coating has an acryloyl group and/or a methacryloyl group in both the resin component and the reactive diluent. This invention relates to a sulfurization-resistant gold and silver thread (hereinafter referred to as gold and silver thread). The present invention is based on the inventors' discovery that a coating layer formed of an ultraviolet curable resin paint, which will be described in detail later, surprisingly exhibits an extremely excellent blocking effect against hydrogen sulfide gas and sulfides. It was completed based on knowledge. Therefore, the gold and silver thread of the present invention is characterized in that the coding layer of the conventional gold and silver thread using a silver vapor deposited layer is formed with an ultraviolet curable resin paint, and the coating layer is resistant to hydrogen sulfide gas or sulfide. It shows an extremely excellent blocking effect against the silver vapor deposited layer, completely preventing discoloration due to sulfurization, and has excellent sulfurization resistance. Moreover, since a silver vapor deposited layer is used, the disadvantages of using other sulfide-resistant metals, such as poor gloss, poor performance other than sulfide resistance, and high cost, are eliminated. Furthermore, the ultraviolet curable resin paint used in the present invention cures without any special heating by simply irradiating it with ultraviolet rays, and provides a relatively flexible coating, so it can be cured at high temperatures during baking, such as when conventional baking paints are used. It solves problems such as yellowing of the surface of the silver vapor deposited layer, easy damage of the support, and hard coating layer with poor texture, and is characterized by the production of extremely high-quality gold and silver threads. Furthermore, since the ultraviolet curable resin coating used in the present invention is solvent-free, it is also excellent from the viewpoint of pollution. The ultraviolet curable resin coating used in the present invention is a coating that can be easily cured within a few seconds to several minutes by irradiation with ultraviolet rays without the need for particular heating to form a flexible and strong coating film. The paint has a resin component,
It contains a reactive diluent and a photopolymerization initiator as essential components, and may also contain various additives such as a coloring agent and a non-reactive resin. The resin component is a polymer or oligomer having at least one addition-polymerizable double bond in its molecule, and may be solid or liquid at room temperature. The liquid resin component can also serve as a reactive diluent. Such polymers or oligomers include unsaturated polyester resins, acryloyl group-reactive resins, allyl group-reactive resins, sol-type resins, thiol/ene-based resins, etc. Acryloyl group-reactive resins give the best results in terms of barrier properties against sulfides, chemical resistance, workability in forming coatings, etc.
It has been found that this meets the objectives of the present invention. Such acryloyl group-reactive resin is
Low molecular weight compounds and polymers that have at least one, preferably two or more acryloyl groups and/or methacryloyl groups in their molecules, such as hydroxyl groups, isocyanate groups, carboxyl groups, epoxy groups, etc. It is obtained by reacting a monomer containing a group and/or a methacryloyl group, and may be obtained by further modifying such a resin with an oil, a fatty acid, or the like. In the following description, the term acryloyl group, acrylate or acrylic is used as a concept that includes methacryloyl group, methacrylate or methacrylic. Specific examples of the acryloyl group-reactive resin include acrylates of simple polyols, side-chain acryloyl group-type acrylic resin prepolymers, telomerized polyester acrylates, telomerized polyamide acrylates, urethane resin acrylates, and silicone resin acrylates. It will be done. The reactive diluent is an addition polymerizable compound that is liquid at room temperature, and has the function of dissolving the resin component and adjusting its viscosity, and also crosslinks the resin component or polymerizes or crosslinks itself. It has the effect of helping to form a strong coating film. Although many such reactive diluents are known, it has been found that acrylic diluents in particular meet the objectives of the present invention.
Specific examples of acrylic diluents include polyethylene glycol diacrylate, 2-ethylhexyl acrylate, tetrahydrofurfuryl acrylate, hydroxypropyl acrylate, diethylene glycol ethyl ether acrylate, diethylene glycol diacrylate,
Neopentyl glycol diacrylate, hydropivalic acid neopentyl ester diacrylate, trimethylolpropane triacrylate,
Examples include 1,6-hexanediol diacrylate, diventaerythritol hexaacrylate, adipate neopentyl ester diacrylate, tetramethylolmethanetetraacrylate, (bisphenol A) bisdiethylene glycol ether diacrylate, and the like. The photopolymerization initiator is a compound that easily generates free radicals when exposed to ultraviolet irradiation, such as benzoyl alkyl ethers, α-acyloxime esters, acetophenones, benzophenones, benzyl ketals, and ketone amines. Compounds such as the following are preferably used. In the ultraviolet curable resin coating used in the present invention, the ratio of the reactive diluent to the resin component is preferably 20 to 150 parts per 100 parts (parts by weight, hereinafter the same) of the resin component. If the proportion of reactive diluent is less than 20 parts, the viscosity of the paint will generally become too high, resulting in poor coating suitability, and the resulting paint film will become too hard, leading to deformation and deterioration of the flexible support. Sometimes. while 150
If the amount exceeds 30%, not only will the curing speed of the paint decrease and productivity will deteriorate, but also the coating performance such as hydrogen sulfide gas and sulfide barrier properties and chemical resistance will deteriorate, and the silver vapor deposited layer and Adhesion to the flexible support may deteriorate, and unreacted reactive diluent may remain in the coating. The photopolymerization initiator is usually used in an amount of about 1 to 8 parts based on 100 parts of the total amount of the resin component and the reactive diluent. In the present invention, the intended purpose is achieved by using an ultraviolet curable resin paint having the composition as described above, but when the following non-reactive resin is further blended into the paint, the leveling of the paint film is improved. It has been found that coating film with uniform thickness can be obtained. Examples of such non-reactive resins include cyclohexanone ketone resins, polyvinyl butyral, cellulose derivatives, polyamide resins, cyclized rubbers, phenolic resins, polyester resins, vinyl acetate resins, acrylic resins,
Examples include silicone resin. The non-reactive resin is usually used in an amount of 40 parts or less based on 100 parts of the resin component. If the amount of non-reactive resin exceeds 40 parts, curing of the paint tends to be poor and the performance of the paint film tends to deteriorate. The ultraviolet curable resin coating used in the present invention may contain additives such as dyes, colorants such as transparent organic pigments, and ultraviolet absorbers as appropriate. Next, the gold and silver threads of the present invention will be explained in order: gold and silver threads (), () and (). First, to explain the gold and silver thread (), the flexible support used is, for example, polyester,
polyamide, polyamideimide, polyethylene,
Examples include films such as polypropylene, polycarbonate, polyvinyl chloride, and cellulose acetate, polymer films such as cellophane, and Japanese paper. Normally, the thickness of polymer film is 6
~50μ, but as Japanese paper, the basis weight is 12~25
About g/m 2 is used. When using a Japanese paper support, apply a filler in advance. The filler is not particularly limited and ordinary resin paints can be used, but the ultraviolet curable resin paint is particularly preferred. The coating amount of the filler is about 3 to 7 g/m 2 (in terms of solid content, the same applies hereinafter). A silver vapor deposited layer is provided on the support directly or after an undercoating layer of the ultraviolet curable resin coating is provided, and a top coating layer of the ultraviolet curable resin coating is formed thereon. The top coating layer and undercoating layer can be formed using an ultraviolet curable resin paint by applying ultraviolet rays after applying the paint, and no particular heating is required. The thickness of the top coating layer and undercoating layer is usually 0.5~2μ
That's about it. For the undercoating layer, if you want to further improve the sulfidation resistance, or if you use a polymer film support that does not have good adhesion to the silver deposited layer, use a transparent polymer film support on the side of the support. If desired, a silver luster that does not change color over time may be provided on either the support side or the top coating layer side. If silver luster is desired only on either the support side or the top coating layer side, either the top coating layer or the undercoating layer may be colored opaque. If metallic luster of various colors other than silver luster is desired, the top coating layer and/or undercoating layer are colored transparent. The silver deposition layer is formed by a conventional method such as a vacuum deposition method, a sputtering method, or an ion plating method, and its thickness is about 0.03 to 0.15 μm. The film-like material obtained as described above is slit to an appropriate width, e.g. 0.15~
Gold and silver thread () can be obtained by slitting it to about 1.5mm. This gold and silver thread may be used as it is as a flat gold and silver thread, or it may be used as a twisted gold and silver thread by twisting it with other threads such as rayon, silk, cotton, Tetron, nylon, etc. good. The gold and silver thread () is made by laminating two films of the film-like material used in the production of the gold and silver thread () with the support inside with adhesive, and then slitting them in the same way as in the case of the gold and silver thread (). available. As the adhesive, adhesives such as vinyl acetate resin, vinyl acetate-ethylene copolymer resin, polyvinyl alcohol, epoxy resin, urethane resin, silicone, and nitrile rubber are used as appropriate. The two-braid structure of gold and silver threads is preferably employed when Japanese paper is used as the support. The gold and silver thread () is made of transparent material as a support, on which an undercoating layer of ultraviolet curable resin paint is provided, followed by a silver vapor deposition layer and, if necessary, a top coating layer of ultraviolet curable resin paint. It can be obtained by bonding two film-like materials with an adhesive with the silver vapor deposited layer (or top coating layer) on the inside and slitting them in the same manner as in the case of gold and silver thread. The above-mentioned polymer film is used as the transparent support. Gold and silver thread () is used to form the undercoating layer, top coating layer, and silver vapor deposition layer.
The process may be the same as in the case of , and the bonding of the film-like material is carried out in the same manner as in the case of gold and silver thread. Since the gold and silver threads of the present invention have excellent sulfidation resistance, they can be suitably used in various products in place of conventional gold and silver threads using vapor-deposited silver layers, and provide products that can permanently maintain excellent silver luster. Next, the gold and silver threads of the present invention will be explained with reference to Examples and Comparative Examples. Example 1 An ultraviolet curable resin paint (A) having the following composition was continuously applied to one side of a long polyethylene terephthalate film with a thickness of 12 μm using a roll coater, and an output of 4 kW was applied while the film was transported at approximately 35 m/min.
(80W/cm) high-pressure mercury lamp [manufactured by Oak Seisakusho Co., Ltd.]
The coating film was cured by irradiating ultraviolet rays at an intensity of 95 mW/cm 2 (illuminance at around 365 nm) using three tubes to form an undercoating layer with a thickness of 1 μm. Ultraviolet curable resin paint (A) [Viscosity 40±5cP (25℃)] Ingredients: Epoxy acrylate resin 40 (Molecular weight 1500, approximately 3 acryloyl groups per 1000 molecular weight) Polyethylene glycol - 400 diacrylate
23 Neopentyl glycol diacrylate 5 Adipate neopentyl ester diacrylate 10 2-Hydroxy-3-phenoxypropyl acrylate 10 2-Hydroxypropyl acrylate 10 Benzophenone 5 p-diethoxyacetophenone 3 Hiraku 11 (Hitachi Chemical Co., Ltd.) Ketone Resin)
5 Cellulose Acetate Ptylate 1 Silicone 200 (ppm) Silver is continuously deposited on the undercoating layer by vacuum evaporation to form a 0.08μ thick silver deposited layer, and on top of that the UV curable resin paint
Added 22 parts of titanium oxide to (A) [hereinafter referred to as
An ultraviolet curable resin coating (referred to as A') was continuously applied and cured in the same manner as described above to form a top coating layer with a thickness of 1 μm. The obtained film-like material is slitted with a micro slitter.
The gold and silver threads were slit to a width of 0.38mm. Example 2 An ultraviolet curable resin coating (B) having the following composition was used instead of the ultraviolet curable resin coating (A), and an ultraviolet curable resin coating (B) was used instead of the ultraviolet curable resin coating (A'). Gold and silver threads were obtained in the same manner as in Example 1, except that 31 parts of titanium oxide was further added to the material (hereinafter referred to as ultraviolet curable resin paint (B')). Ultraviolet curable resin paint (B) [Viscosity 45±5cP (25℃)] Ingredients Urethane acrylate resin 45 (Molecular weight 1500, approximately 2 acryloyl groups per 1000 molecular weight) Polyethylene glycol - 400 diacrylate
28 Neopentyl glycol diacrylate 10 Tetrahydrofurfuryl acrylate 20 Benzyl ketal 5 Polyvinyl petyral 3 Cellulose acetate 1 Silicone 200 (ppm) Example 3 Top coating layer was coated with ultraviolet curable resin paint
Gold and silver threads were obtained in the same manner as in Example 1 except that (A) was used. Example 4 Gold and silver threads were obtained in the same manner as in Example 1, except that the undercoating layer was omitted and the top coating layer was formed using an ultraviolet curable resin paint (A). Example 5 On one side of Mitsumata-containing washi paper with a basis weight of 18 g/ m2, an amount of UV-curable resin paint (A) was applied as a sealant to 6 g/m2.
m 2 and cured as in Example 1. A film-like product was prepared in the same manner as in Example 1, except that the washi paper coated with the filler was used instead of a polyethylene terephthalate film and the top coating layer was formed using an ultraviolet curable resin paint (A). This was slit in the same manner as in Example 1 to obtain gold and silver thread. Example 6 Two sheets of the film obtained in Example 5 were pasted together using a vinyl acetate resin adhesive with Japanese paper on the inside, and then slit in the same manner as in Example 1 to obtain gold and silver threads. Example 7 A film-like material was prepared in the same manner as in Example 1 except that the top coating layer was omitted, and two sheets of this were pasted together using a urethane resin adhesive with the silver vapor deposited layer inside, and then Example 1 was prepared. I slit it in the same way as I did and got gold and silver thread. The gold and silver threads obtained in Examples 1 to 7 have no deformation or alteration in the support, exhibit the excellent silver luster inherent to pure silver, have excellent texture, and are of extremely high quality. It was hot. Comparative Example 1 The under coating layer and top coating layer were coated with amino alkyd resin paint,
Gold and silver threads were obtained in the same manner as in Example 1, except that they were formed by baking at ℃ for 38 seconds. The obtained gold and silver threads showed deformation and alteration in the support, yellowing of the silver deposited layer and loss of silver luster.
Moreover, the texture was inferior. The gold and silver threads obtained in Examples 1 to 7 and Comparative Example 1 were tested for hydrogen sulfide. The hydrogen sulfide test was performed by leaving the sample in a zero atmosphere at a temperature of 20° C., 95% RH, and a hydrogen sulfide concentration of 0.6% by weight for 72 hours. After the test, changes in the luster of the gold and silver threads were observed. The gloss was evaluated using the following 5-level evaluation. Evaluation value 5 Very good (pure silver luster) 4 Good 3 Fairly good 2 Fairly poor 1 Poor The gloss was observed in Examples 1 to 2 and Comparative Example 1.
In the case of the gold and silver threads in Examples 4 and 5, the procedure was carried out on the support side, in the case of the gold and silver threads in Examples 4 and 5, it was carried out on the top coating layer side, and in the case of the gold and silver threads in Examples 3 and 6 and 7, it was carried out on both sides, but the same procedure was carried out. obtained an evaluation value of
The results are shown in Table 1. Table 1 also shows the results of measuring the abrasion resistance and light resistance of the film-like material before slitting it into gold and silver threads, and the results of examining the gloss and texture of the gold and silver threads. The abrasion resistance test was conducted using a Gakushin type reciprocating abrasion test (manufactured by Uenoyama Kiko Co., Ltd.) under the conditions of a load of 200 g and 30 reciprocations (minutes). The above light resistance test is JIS
It was carried out according to L 0841. The texture was evaluated using the following 5-level evaluation. Evaluation value 5 Very good 4 Good 3 Fairly good 2 Fairly poor 1 Poor Comparative example 2 Same as Example 1 except that the under coating layer and top coating layer were formed by using acrylic resin paint and baking at 180°C for 30 seconds. In the same way, he obtained gold and silver thread. Comparative Example 3 Gold and silver threads were obtained in the same manner as in Example 1, except that the undercoating layer and top coating layer were formed by baking at 180° C. for 30 seconds using urethane resin paint. Comparative Example 4 Undercoating layer and top coating layer were coated with urea-melamine resin paint at 180°C.
Gold and silver threads were obtained in the same manner as in Example 1, except that they were formed by baking for 30 seconds. Comparative Example 5 Gold and silver threads were obtained in the same manner as in Example 1, except that the undercoating layer and top coating layer were formed by baking at 180° C. for 30 seconds using an epoxy resin paint. Comparative Example 6 The under coating layer and top coating layer were coated with 180% nitrocellulose resin paint.
Gold and silver threads were obtained in the same manner as in Example 1, except that they were formed by drying at ℃ for 30 seconds. The same tests as above were conducted on the gold and silver threads obtained in Comparative Examples 2 to 6 and the film-like products before slitting. The results are shown in Table 1.
【表】【table】
Claims (1)
脂塗料の硬化塗膜であるアンダーコーテイング層
を介して銀蒸着層を設け、そのうえに紫外線硬化
性樹脂塗料の硬化塗膜であるトツプコーテイング
層を設けてなるフイルム状物のスリツト糸であつ
て、かつ前記紫外線硬化性樹脂塗料が樹脂成分お
よび反応性稀釈剤のいずれもがアクリロイル基お
よび（または）メタクリロイル基を有するもので
あることを特徴とする耐硫化性金銀糸。 ２ 紫外線硬化性樹脂塗料が非反応性樹脂を含有
するものである特許請求の範囲第１項記載の金銀
糸。 ３ 支持体が高分子フイルムである特許請求の範
囲第１項記載の金銀糸。 ４ 支持体が目止剤を塗布、硬化した和紙である
特許請求の範囲第１項記載の金銀糸。 ５ 目止剤が樹脂成分および反応性稀釈剤のいず
れもがアクリロイル基および（または）メタクリ
ロイル基を有するものからなる紫外線硬化性樹脂
塗料である特許請求の範囲第４項記載の金銀糸。 ６ 可撓性支持体上に直接または紫外線硬化性樹
脂塗料の硬化塗膜であるアンダーコーテイング層
を介して金蒸着層を設け、そのうえに紫外線硬化
性樹脂塗料の硬化塗膜であるトツプコーテイング
層を設けてなるフイルム状物を２枚該支持体を内
側にして接着剤で貼合わせたもののスリツト糸で
あつて、かつ前記紫外線硬化樹脂塗料が樹脂成分
および反応性稀釈剤のいずれもがアクリロイル基
および（または）メタクリロイル基を有するもの
であることを特徴とする耐硫化性金銀糸。 ７ 紫外線硬化性樹脂塗料が非反応性樹脂を含有
するものである特許請求の範囲第６項記載の金銀
糸。 ８ 支持体が目止剤を塗布、硬化した和紙である
特許請求の範囲第６項記載の金銀糸。 ９ 目止剤が樹脂成分および反応性稀釈剤のいず
れもがアクリロイル基および（または）メタクリ
ロイル基を有するものからなる紫外線硬化性樹脂
塗料である特許請求の範囲第８項記載の金銀糸。 １０ 透明な可撓性支持体上に紫外線硬化性樹脂
塗料の硬化塗膜であるアンダーコーテイング層を
介して銀蒸着層を設けてなるフイルム状物を２枚
該銀蒸着層を内側にして接着剤で貼合わせたもの
のスリツト糸であつて、かつ前記紫外線硬化性樹
脂塗料が樹脂成分および反応性稀釈剤のいずれも
がアクリロイル基および（または）メタクリロイ
ル基を有するものであることを特徴とする耐硫化
金銀糸。 １１ 銀蒸着層上にさらに樹脂成分および反応性
稀釈剤のいずれもがアクリロイル基および（また
は）メタクリロイル基を有するものからなる紫外
線硬化性樹脂塗料の硬化塗膜であるトツプコーテ
イング層を設けてなる特許請求の範囲第１０項記
載の金銀糸。 １２ 紫外線硬化性樹脂塗料が非反応性樹脂を含
有するものである特許請求の範囲第１０項または
第１１項記載の金銀糸。[Scope of Claims] 1. A silver vapor-deposited layer is provided on a flexible support directly or via an undercoating layer which is a cured coating of an ultraviolet curable resin coating, and a cured coating of an ultraviolet curable resin coating is provided on the flexible support. A slit yarn of a film-like material provided with a certain top coating layer, and the ultraviolet curable resin coating has an acryloyl group and/or a methacryloyl group in both the resin component and the reactive diluent. A sulfide-resistant gold and silver thread. 2. The gold and silver thread according to claim 1, wherein the ultraviolet curable resin coating contains a non-reactive resin. 3. The gold and silver thread according to claim 1, wherein the support is a polymer film. 4. The gold and silver thread according to claim 1, wherein the support is Japanese paper coated with a filler and cured. 5. The gold and silver thread according to claim 4, wherein the filler is an ultraviolet curable resin coating in which both the resin component and the reactive diluent have an acryloyl group and/or a methacryloyl group. 6. A gold vapor deposited layer is provided on the flexible support directly or via an undercoating layer which is a cured coating of an ultraviolet curable resin coating, and a top coating layer which is a cured coating of an ultraviolet curable resin coating is provided thereon. It is a slit thread made by laminating two film-like materials with the support inside with an adhesive, and the ultraviolet curable resin coating has a resin component and a reactive diluent both containing acryloyl groups and ( or) A sulfide-resistant gold and silver thread having a methacryloyl group. 7. The gold and silver thread according to claim 6, wherein the ultraviolet curable resin coating contains a non-reactive resin. 8. The gold and silver thread according to claim 6, wherein the support is Japanese paper coated with a filler and cured. 9. The gold and silver thread according to claim 8, wherein the filler is an ultraviolet curable resin coating in which both the resin component and the reactive diluent have an acryloyl group and/or a methacryloyl group. 10 Two film-like materials each having a silver vapor-deposited layer provided on a transparent flexible support through an undercoating layer, which is a cured film of an ultraviolet curable resin paint, with the silver vapor-deposited layer on the inside, and an adhesive. The sulfurization-resistant sulfur-resistant material is a slit yarn of a material pasted together, and the ultraviolet curable resin coating is characterized in that both the resin component and the reactive diluent have an acryloyl group and/or a methacryloyl group. Gold and silver thread. 11 A patent in which a top coating layer is further provided on the silver vapor deposited layer, which is a cured coating film of an ultraviolet curable resin paint consisting of a resin component and a reactive diluent each having an acryloyl group and/or a methacryloyl group. Gold and silver thread according to claim 10. 12. The gold and silver thread according to claim 10 or 11, wherein the ultraviolet curable resin coating contains a non-reactive resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10962080A JPS5735025A (en) | 1980-08-09 | 1980-08-09 | Sulfurization resistant tinsel yarn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10962080A JPS5735025A (en) | 1980-08-09 | 1980-08-09 | Sulfurization resistant tinsel yarn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5735025A JPS5735025A (en) | 1982-02-25 |
| JPS6153448B2 true JPS6153448B2 (en) | 1986-11-18 |
Family
ID=14514900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10962080A Granted JPS5735025A (en) | 1980-08-09 | 1980-08-09 | Sulfurization resistant tinsel yarn |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5735025A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6282374B1 (en) * | 2017-09-11 | 2018-02-21 | 尾池工業株式会社 | Black vapor deposition film and method for producing the same |
-
1980
- 1980-08-09 JP JP10962080A patent/JPS5735025A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5735025A (en) | 1982-02-25 |
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