JPS6221920B2 - - Google Patents
Info
- Publication number
- JPS6221920B2 JPS6221920B2 JP2257880A JP2257880A JPS6221920B2 JP S6221920 B2 JPS6221920 B2 JP S6221920B2 JP 2257880 A JP2257880 A JP 2257880A JP 2257880 A JP2257880 A JP 2257880A JP S6221920 B2 JPS6221920 B2 JP S6221920B2
- Authority
- JP
- Japan
- Prior art keywords
- aqueous dispersion
- paper
- polyvinyl alcohol
- metal
- film
- 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
- 239000006185 dispersion Substances 0.000 claims description 40
- 229920005672 polyolefin resin Polymers 0.000 claims description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000000123 paper Substances 0.000 description 20
- 229920001577 copolymer Polymers 0.000 description 14
- -1 zinc. α Chemical class 0.000 description 10
- 239000002245 particle Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000002932 luster Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 229920000554 ionomer Polymers 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000001846 repelling effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 229920006027 ternary co-polymer Polymers 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 2
- 229920001112 grafted polyolefin Polymers 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000218202 Coptis Species 0.000 description 1
- 244000062175 Fittonia argyroneura Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Description
本発明は、金属蒸着紙の製造方法に関する。更
に詳しくは、表面金属光沢性が改善された金属蒸
着紙の製造方法に関する。
本出願人らは先に、紙の少くとも一面に合成樹
脂層および金属蒸着層を順次形成させた金属蒸着
紙およびその製造方法についての特許出願を行な
い、かかる金属蒸着紙は、紙の少くとも一面に合
成樹脂の水性分散液を塗布し、該合成樹脂の成膜
温度以上で乾燥させた後、その被膜上に金属層を
真空蒸着させることにより製造されることを開示
している（特願昭54−81298号参照）。
この方法において、塗布に必要な水性分散液の
全量を一回で塗布すると透湿度および表面光沢の
向上がみられないので、この塗布を複数回に分け
て行なうとそのような欠点が解消することが判明
している。しかるに、このような塗布を数回にわ
たつて行なう場合、それ以前の塗布で形成された
樹脂被膜上に適用された水性分散液ははじかれ
て、そこに均一な被膜を形成し難い現象がみられ
る。そして、このような不均一な被膜上に金属蒸
着層を形成させると、蒸着膜本来の金属光沢が失
われ、白化し易い傾向を示す。
本発明者らは、金属固有の光沢を示す金属蒸着
紙の形成を阻害するかかるはじき現象を回避し得
る対策について種々検討の結果、水性分散液中に
ボリビニルアルコールを添加することにより、こ
のような課題が解決できることを見出した。この
ような効果は、ポリビニルアルコールにのみみら
れる独特の効果であり、同様に水溶性の高分子物
質であるでん粉やメチルセルロースの場合には、
そのような効果が認められないかあるいは水性分
散液との均一な混合を不可能とする。
従つて、本発明は金属蒸着紙の製造方法に係
り、金属蒸着紙は界面活性剤を含有しないポリオ
レフイン系樹脂水性分散液にポリビニルアルコー
ルを全樹脂重量の約0.03〜10％の割合で添加し、
そこに形成されたポリビニルアルコール混合水性
分散液を紙に塗布、乾燥させた後、その塗布面上
に金属を真空蒸着させることにより製造される。
界面活性剤を含有しないポリオレフイン系樹脂
水性分散液は、ポリオレフイン系樹脂自身が自己
の有する分散能によつて、ほぼ球状の粒子として
水性媒体中に均一に分散し、水性分散液を形成す
る。かかる自己分散性のポリオレフイン系樹脂
は、オレフインの単独重合体または相互共重合
体、オレフインとビニル化合物との共重合体など
で、これら重合体中に分散能を付与するカルボキ
シル基含有または形成性共単量体を共重合させ、
含有している。
好ましい自己分散性ポリオレフイン系樹脂は、
エチレンによつて代表されるオレフインとα，β
―エチレン性不飽和カルボン酸またはその誘導体
との共重合体、またはオレフイン重合体の不飽和
カルボン酸またはその誘導体のグラフト共重合体
であり、共重合体中の遊離のカルボキシル基は完
全にまたは部分的にナトリウム、カリウムなどの
アルカリ金属または亜鉛などのアルカリ土類金属
で中和されている。
α，β―エチレン性不飽和カルボン酸およびそ
の誘導体としては、アクリル酸、メタクリル酸、
クロトン酸、マレイン酸およびこれらの酸無水物
やけん化されてカルボキシル基を形成するエステ
ル、酸アミド、酸イミドなどが例示でき、これら
は共重合体中に約５〜45重量％、好ましくは約10
〜20重量％の割合で共重合されている。この共重
合割合がこれより少ないと水分分散能が劣り、粒
径の小さい分散液が得られ難い。一方これにより
多い共重合割合では、共重合体の融点が低すぎて
被膜が弱く、耐水性も低下する。グラフト共重合
体の場合には、その共重合割合は前記割合よりも
一桁程度少なくてもよい。
水性分散液が調製されるポリオレフイン系樹脂
としては、そこに蒸着されるアルミニウムなどの
金属に対する接着性の点などから、特にアイオノ
マー樹脂、α，β―不飽和カルボン酸グラフトポ
リオレフインなどが好んで用いられる。アイオノ
マー樹脂は、カルボキシル基の全部または一部が
ナトリウム、亜鉛などの金属でイオン化されてい
るため、水に対して容易に自己分散する性質を有
しているので、それ自体で水性分散液を形成し得
る。アイオノマー樹脂、例えばエチレン―メタク
リル酸共重合体のナトリウム塩の水性分散液は、
それ単独で用いられるだけではなく、そこに例え
ばエチレン―酢酸ビニル共重合体、ポリエチレン
などを均一に混合するだけで、本来自己分散性を
有しないポリオレフイン系樹脂との混合水性分散
液を形成することができ、かかる混合水性分散液
もまた自己分散性のポリオレフイン系樹脂水性分
散液として使用することができる。
α，β―不飽和カルボン酸グラフトポリオレフ
インは、その溶融物を塩基性物質を含有する加熱
水中に撹拌下に添加することによつて、容易にそ
の水性分散液を形成させることができる（特開昭
52−13539号公報参照）。この際、エチレン―酢酸
ビニル共重合体、ポリエチレンなどとの混合物を
同様に処理すると、これらの非自己分散性ポリオ
レフイン系樹脂との混合水性分散液を形成させる
ことができる。具体的には、例えば酸価約30〜
150のα，β―不飽和カルボン酸グラフトポリオ
レフイン50〜１重量部にエチレン―酢酸ビニル共
重合体、ポリエチレンなどを50〜99重量部混合
し、その溶融均一混合物を塩基性物質を含有する
加熱水中に撹拌しながら添加することにより、容
易に混合水性分散液を形成させることができる。
このように、非自己分散性ポリオレフイン系樹脂
との混合水性分散液も、アイオノマー樹脂の混合
水性分散液と同様に、自己分散性のポリオレフイ
ン系樹脂水性分散液として使用することができ
る。
非自己分散性のポリオレフイン系樹脂として挙
げられるには、エチレン、プロピレン、１―ブテ
ン、４―メチル―１―ペンテンなどのα―オレフ
インの単独重合体または共重合体であり、例えば
ポリエチレン、ポリプロピレン、ポリ―１―ブテ
ン、ポリ―４―メチル―１―ペンテンなどの単独
重合体、またはエチレン―プロピレン共重合体、
エチレン―１―ブテン共重合体、エチレン―ブタ
ジエン共重合体、エチレン―プロピレン―ブタジ
エン３元共重合体、エチレン―プロピレン―ジシ
クロペンタジエン３元共重合体、エチレン―プロ
ピレン―エチリデンノルボルネン３元共重合体、
プロピレン―１―ブテン共重合体、プロピレン―
ブタジエン共重合体、エチレン―酢酸ビニル共重
合体またはそのけん化物などの樹脂状またはゴム
状共重合体が挙げられ、これらは単独でまたは２
種以上の混合物として使用することができる。
このようにして調製される自己分散性のポリオ
レフイン系樹脂水性分散液は、固形分濃度が約10
〜60重量％、好ましくは約20〜50重量％のときに
塗布に適した粘度を有し、また被膜にピンホール
が発生するのを防止することができる。その際、
必要ならば更に増粘剤を加えて粘度を調節し、紙
への浸透を最小限に抑えることも可能である。
これらのポリオレフイン系樹脂の水性分散液
は、自己分散性のポリオレフイン系樹脂から調製
されているので、そこに実質的に揮発性の添加
剤、特に界面活性剤を含有していない。乳化剤や
分散剤として作用する界面活性剤や重合時の各種
添加剤などの揮発性添加剤の存在は、金属蒸着の
際に必要とする高真空度を得ることを困難とさせ
るばかりでなく、金属蒸着面の光沢度に著しく悪
影響を及ぼす不均一被膜の形成をもたらし、更に
は金属蒸着面の接着性や印刷適性などにも悪影響
を与えるので、その存在量を最小限に留める配慮
が特に望まれる。
ポリビニルアルコールは、通常常市販されてい
るものがそのまま使用できる。例えば、ポリ酢酸
ビニルをけん化度80％以上けん化したもの、４％
水溶液としたときの粘度が5cps（20℃）以上の
もの、水洗や真空乾燥などの処理手段で不純物や
揮発性成分を除去したものなどが好んで用いられ
る。また、必要に応じて、アクリル酸や無水マレ
イン酸などのα，β―不飽和カルボン酸またはそ
の誘導体とのランダムあるいはグラフト共重合
体、更にはエチレンとのランダム共重合体として
使用することができる。
このようなポリビニルアルコールは、ポリオレ
フイン系樹脂水性分散液に固体状のまま添加して
溶解させたり、あるいは約１〜20％の水溶液の状
態で添加し、そこに均一なポリビニルアルコール
混合水性分散液を形成させて使用される。添加の
割合としては、ポリビニルアルコールが全樹脂重
量（ポリオレフイン系樹脂とポリビニルアルコー
ルの合計重量）の約0.03〜10％、好ましくは約
0.1〜５％の範囲が選択される。添加割合がこれ
より少ないとはじき現象が回避されず、一方これ
より多い添加割合では塗布被膜が白濁し、その塗
布面上に真空蒸着された金属蒸着面が白化し、金
属光沢が低下して蒸着金属本来の色調と全く異な
つた色調の金属蒸着面を与える。
上質紙、模造紙、クレーコート紙、クラフト
紙、アート紙などの各種の紙へのポリビニルアル
コール混合水性分散液の塗布は、スプレー法、ロ
ールコーター法など公知の方法で、連続的かつ均
一に行なうことができ、紙に対して約１〜30ｇ／
m2、好ましくは約２〜15ｇ／m2の全樹脂塗布量で
塗布する。塗布面の表面が平滑でないと、金属蒸
着面の光沢が乏しく、防湿性も劣る傾向がみられ
るので、塗布面が鏡面状態にあることが望まし
い。鏡面仕上げをロールなどによつて行なうと、
むらが生ずるのを避けることができなので、少な
い樹脂量で複数回くり返して重ね塗りする方法が
特に好ましい。この重ね塗りの場合には、水性分
散液中にポリビニルアルコールが添加されている
ので、既に形成されている被膜によつて新たに適
用した水性分散液がはじかれるような現象はもは
やみられない。
塗布されたポリビニルアルコール混合水性分散
液の乾燥は、ポリオレフイン系樹脂およびポリビ
ニルアルコール混合の混合物の成膜温度以上、例
えば室温乃至約200℃、一般にはこれら混合物の
軟化点または融点以上の温度で行われる。乾燥条
件は、水性分散液中のポリオレフイン系樹脂粒子
の粒径によつても影響され、大きな粒径の場合は
比較的高温で、まさ小さな粒径の場合には比較的
低温で乾燥される。そして、一般には100℃以上
の温度で数秒間〜数分間程度で行われる。
形成される被膜の厚さは、紙の種類や用途など
に応じて、一般に約１〜30μ、好ましくは約２〜
15μ程度であり、この範囲内の厚さのものは水性
分散液中の固形分濃度および粒径を調節すること
によつて、容易に均一な被膜として得られる。
真空蒸着は、10-3〜10-5mmＨｇ程度の高真空度
下において、蒸着すべき金属をその融点以上に加
熱することにより行われる。蒸着金属としては、
アルミニウム、亜鉛、銅、銀、鉛、マンガンなど
が用いられ、蒸着条件を調節することによつて約
100〜1000Å、好ましくは約300〜700Å程度の金
属蒸着膜を形成させる。形成された金属蒸着膜の
樹脂被膜を介しての紙への接着性は良好であり、
セロフアンテープ剥離試験にも十分に耐える程で
ある。
通常のプラスチツクフイルムへ金属蒸着させる
場合には、プラスチツクフイルムを予めコロナ放
電処理などをしないと金属は強固に接着しない
が、本発明の金属蒸着紙は何ら前処理を施さなく
ともこのように良好な接着性を有している。
本発明に係る金属蒸着紙は、菓子やタバコの包
装紙として、またレーベル、金銀糸などの用途に
それぞれ有効に利用することができる。そして、
それらの用途に応じて金属蒸着面にエンボス加工
を施したり、あるいはその面の変色に備えた保護
層を形成させることもできる。
次に、実施例について本発明を説明する。
実施例
ポリオレフイン系樹脂としてエチレン―メタク
リル酸共重合体のナトリウム塩（メタクリル酸含
量15重量％、密度0.95ｇ／cm3、中和度59モル％）
を用い、固形分濃度20％、粒径約0.1μの水性分
散液を調製した。一方、ポリビニルアルコール
（クラレ製＃Ｈ、重合度1700、けん化度約99.9
％、４％水溶液としての粘度約30cps）は、10％
溶液として用い、これを前記水性分散液中に後記
表に示されるような割合で加えた。
形成されたポリビニルアルコール混合水性分散
液を、ロールコーターを用いて１回につき２ｇ／
m2の固形分量で上質紙上に３回の重ね塗りを行つ
たが、塗布面上でのはじき現象はみられなかつ
た。塗膜を120℃で乾燥させた後、10mmHgに調整
した真空蒸着装置内において真空蒸着を行ない、
塗布面上にアルミニウム層を約500Åの厚さに形
成させ、その表面光沢度を測定した。光沢度の測
定は、自動式変角光沢計VG―107A（日本電色工
業製）を使用し、投光角および受光角をそれぞれ
45゜で測定して行われた。
The present invention relates to a method for manufacturing metallized paper. More specifically, the present invention relates to a method for producing metallized paper with improved surface metallic gloss. The present applicants previously filed a patent application for a metallized paper in which a synthetic resin layer and a metallized layer are sequentially formed on at least one side of the paper, and a method for manufacturing the same. The patent discloses that it is manufactured by applying an aqueous dispersion of a synthetic resin to one surface, drying it at a temperature higher than the film-forming temperature of the synthetic resin, and then vacuum-depositing a metal layer on the film (patent application). (See No. 1981-81298). In this method, if the entire amount of aqueous dispersion required for coating is applied at one time, no improvement in moisture permeability or surface gloss will be observed, so such drawbacks can be overcome by dividing this application into multiple times. It is clear that However, when such coating is performed several times, the aqueous dispersion applied to the resin film formed by the previous coating is repelled, making it difficult to form a uniform film there. It will be done. When a metal vapor deposition layer is formed on such a non-uniform film, the metal luster inherent to the vapor deposition film is lost, and the film tends to whiten. The inventors of the present invention have investigated various measures to avoid such a repelling phenomenon that inhibits the formation of metal-deposited paper that exhibits the luster inherent to metals. We have discovered that this problem can be solved. This effect is a unique effect found only in polyvinyl alcohol, and similarly in the case of starch and methylcellulose, which are water-soluble polymer substances,
Either no such effect is observed or uniform mixing with the aqueous dispersion is impossible. Therefore, the present invention relates to a method for producing metallized paper, which comprises adding polyvinyl alcohol to an aqueous polyolefin resin dispersion containing no surfactant in a proportion of about 0.03 to 10% of the total resin weight;
It is manufactured by coating the polyvinyl alcohol mixed aqueous dispersion formed thereon on paper, drying it, and then vacuum-depositing a metal onto the coated surface. An aqueous polyolefin resin dispersion containing no surfactant is uniformly dispersed in an aqueous medium as substantially spherical particles due to the dispersion ability of the polyolefin resin itself, thereby forming an aqueous dispersion. Such self-dispersing polyolefin resins include homopolymers or copolymers of olefins, copolymers of olefins and vinyl compounds, and these polymers contain carboxyl group-containing or forming copolymers that impart dispersibility. Copolymerize monomers,
Contains. Preferred self-dispersing polyolefin resins are:
Olefins represented by ethylene and α,β
- copolymers with ethylenically unsaturated carboxylic acids or derivatives thereof, or graft copolymers of unsaturated carboxylic acids or derivatives thereof of olefin polymers, in which the free carboxyl groups in the copolymer are completely or partially It is generally neutralized with alkali metals such as sodium and potassium or alkaline earth metals such as zinc. α,β-Ethylenically unsaturated carboxylic acids and their derivatives include acrylic acid, methacrylic acid,
Examples include crotonic acid, maleic acid, their acid anhydrides, esters, acid amides, and acid imides which are saponified to form carboxyl groups, and these are contained in the copolymer in an amount of about 5 to 45% by weight, preferably about 10% by weight.
It is copolymerized at a rate of ~20% by weight. If the copolymerization ratio is less than this, the water dispersion ability will be poor and it will be difficult to obtain a dispersion liquid with a small particle size. On the other hand, if the copolymerization ratio is higher than this, the melting point of the copolymer will be too low, resulting in a weak coating and poor water resistance. In the case of a graft copolymer, the copolymerization ratio may be about one order of magnitude smaller than the above ratio. As the polyolefin resin from which the aqueous dispersion is prepared, ionomer resins, α,β-unsaturated carboxylic acid graft polyolefins, etc. are particularly preferably used from the viewpoint of adhesion to metals such as aluminum deposited thereon. . Ionomer resin has all or part of its carboxyl groups ionized with metals such as sodium and zinc, so it has the property of easily self-dispersing in water, so it forms an aqueous dispersion by itself. It is possible. An aqueous dispersion of an ionomer resin, such as the sodium salt of ethylene-methacrylic acid copolymer,
Not only can it be used alone, but it can also be used by uniformly mixing ethylene-vinyl acetate copolymer, polyethylene, etc., to form a mixed aqueous dispersion with a polyolefin resin that does not inherently have self-dispersibility. Such a mixed aqueous dispersion can also be used as a self-dispersing polyolefin resin aqueous dispersion. An aqueous dispersion of α,β-unsaturated carboxylic acid-grafted polyolefin can be easily formed by adding the melt into heated water containing a basic substance under stirring (JP-A Akira
52-13539). At this time, by similarly treating a mixture with ethylene-vinyl acetate copolymer, polyethylene, etc., it is possible to form a mixed aqueous dispersion with these non-self-dispersing polyolefin resins. Specifically, for example, an acid value of about 30~
50 to 1 part by weight of α,β-unsaturated carboxylic acid grafted polyolefin No. 150 is mixed with 50 to 99 parts by weight of ethylene-vinyl acetate copolymer, polyethylene, etc., and the molten homogeneous mixture is poured into heated water containing a basic substance. A mixed aqueous dispersion can be easily formed by adding the mixture with stirring.
In this way, a mixed aqueous dispersion with a non-self-dispersing polyolefin resin can also be used as a self-dispersing polyolefin resin aqueous dispersion, similar to a mixed aqueous dispersion of an ionomer resin. Non-self-dispersing polyolefin resins include homopolymers or copolymers of α-olefins such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, such as polyethylene, polypropylene, Homopolymers such as poly-1-butene and poly-4-methyl-1-pentene, or ethylene-propylene copolymers,
Ethylene-1-butene copolymer, ethylene-butadiene copolymer, ethylene-propylene-butadiene ternary copolymer, ethylene-propylene-dicyclopentadiene ternary copolymer, ethylene-propylene-ethylidene norbornene ternary copolymer Union,
Propylene-1-butene copolymer, propylene-
Examples include resinous or rubbery copolymers such as butadiene copolymer, ethylene-vinyl acetate copolymer, or saponified products thereof, which may be used alone or in combination.
It can be used as a mixture of more than one species. The self-dispersing polyolefin resin aqueous dispersion prepared in this manner has a solid content concentration of approximately 10
When the amount is about 60% by weight, preferably about 20 to 50% by weight, it has a viscosity suitable for coating and can prevent pinholes from forming in the film. that time,
If necessary, additional thickeners can be added to adjust the viscosity and minimize penetration into the paper. Since these aqueous dispersions of polyolefin resins are prepared from self-dispersing polyolefin resins, they do not substantially contain volatile additives, particularly surfactants. The presence of volatile additives, such as surfactants that act as emulsifiers and dispersants, and various additives during polymerization, not only makes it difficult to obtain the high degree of vacuum required during metal deposition, but also makes it difficult to obtain the high degree of vacuum necessary for metal deposition. It causes the formation of a non-uniform film that has a significant negative effect on the glossiness of the metal-deposited surface, and also has a negative effect on the adhesion and printability of the metal-deposited surface, so it is particularly desirable to minimize its amount. . As polyvinyl alcohol, commercially available polyvinyl alcohol can be used as is. For example, polyvinyl acetate saponified with a saponification degree of 80% or more, 4%
Those with a viscosity of 5 cps (20°C) or more when made into an aqueous solution, and those whose impurities and volatile components have been removed by processing methods such as washing with water or vacuum drying are preferably used. In addition, if necessary, it can be used as a random or graft copolymer with α,β-unsaturated carboxylic acid or its derivatives such as acrylic acid or maleic anhydride, or further as a random copolymer with ethylene. . Such polyvinyl alcohol can be added as a solid to an aqueous polyolefin resin dispersion and dissolved therein, or added in the form of an approximately 1-20% aqueous solution, and then a homogeneous polyvinyl alcohol mixed aqueous dispersion is added thereto. Formed and used. The proportion of polyvinyl alcohol added is approximately 0.03 to 10% of the total resin weight (total weight of polyolefin resin and polyvinyl alcohol), preferably approximately
A range of 0.1-5% is selected. If the addition ratio is lower than this, the repelling phenomenon will not be avoided, while if the addition ratio is higher than this, the coating film will become cloudy, the metal deposition surface that was vacuum-deposited on the coating surface will become white, and the metallic luster will decrease, making it difficult to deposit. To provide a metal vapor-deposited surface with a color tone completely different from the original color tone of the metal. The polyvinyl alcohol mixed aqueous dispersion is applied continuously and uniformly to various types of paper such as high-quality paper, imitation paper, clay coated paper, kraft paper, and art paper using known methods such as spraying and roll coater methods. Approximately 1-30g/paper
m 2 , preferably at a total resin coverage of about 2 to 15 g/m 2 . If the surface of the coated surface is not smooth, the metal vapor-deposited surface tends to have poor gloss and moisture resistance, so it is desirable that the coated surface has a mirror finish. If mirror finishing is done using a roll, etc.
Particularly preferred is a method of repeating multiple coats using a small amount of resin, since unevenness can be avoided. In the case of this overcoating, since polyvinyl alcohol is added to the aqueous dispersion, there is no longer a phenomenon in which the newly applied aqueous dispersion is repelled by the already formed film. Drying of the applied polyvinyl alcohol mixed aqueous dispersion is carried out at a temperature higher than the film forming temperature of the polyolefin resin and polyvinyl alcohol mixed mixture, for example room temperature to about 200°C, generally at a temperature higher than the softening point or melting point of these mixtures. . The drying conditions are also influenced by the particle size of the polyolefin resin particles in the aqueous dispersion; large particle sizes are dried at relatively high temperatures, and small particle sizes are dried at relatively low temperatures. Generally, this is carried out at a temperature of 100° C. or higher for several seconds to several minutes. The thickness of the film formed is generally about 1 to 30μ, preferably about 2 to 30μ, depending on the type of paper and its use.
The thickness is approximately 15 μm, and a uniform film having a thickness within this range can be easily obtained by adjusting the solid content concentration and particle size in the aqueous dispersion. Vacuum deposition is performed by heating the metal to be deposited to a temperature above its melting point under a high degree of vacuum of about 10 -3 to 10 -5 mmHg. As a vapor deposited metal,
Aluminum, zinc, copper, silver, lead, manganese, etc. are used, and by adjusting the deposition conditions, approximately
A metal vapor deposited film having a thickness of about 100 to 1000 Å, preferably about 300 to 700 Å is formed. The adhesion of the formed metal vapor-deposited film to paper through the resin film is good;
It sufficiently withstands cellophane tape peeling test. When depositing metal onto ordinary plastic film, the metal does not adhere firmly unless the plastic film is subjected to corona discharge treatment, etc., but the metal-deposited paper of the present invention has such good properties even without any pretreatment. It has adhesive properties. The metallized paper according to the present invention can be effectively used as wrapping paper for confectionery and cigarettes, as well as for labels, gold and silver threads, and the like. and,
Depending on the application, the metal-deposited surface may be embossed, or a protective layer may be formed to prevent discoloration of the surface. Next, the present invention will be explained with reference to examples. Example Sodium salt of ethylene-methacrylic acid copolymer as polyolefin resin (methacrylic acid content 15% by weight, density 0.95 g/cm 3 , degree of neutralization 59 mol%)
An aqueous dispersion with a solid content concentration of 20% and a particle size of approximately 0.1μ was prepared using On the other hand, polyvinyl alcohol (#H manufactured by Kuraray, degree of polymerization 1700, degree of saponification approximately 99.9)
%, viscosity as a 4% aqueous solution approximately 30 cps) is 10%
This was used as a solution and added to the aqueous dispersion in the proportions shown in the table below. The formed polyvinyl alcohol mixed aqueous dispersion was coated with a roll coater at a rate of 2 g/time.
Three coats were applied on high-quality paper at a solid content of m 2 , but no repellency was observed on the coated surface. After drying the coating film at 120℃, vacuum evaporation is performed in a vacuum evaporation device adjusted to 10mmHg.
An aluminum layer with a thickness of about 500 Å was formed on the coated surface, and its surface gloss was measured. Glossiness was measured using an automatic variable angle gloss meter VG-107A (manufactured by Nippon Denshoku Kogyo), and measuring the emission angle and reception angle respectively.
Measurements were made at 45°.
【表】
形成された塗膜にはじき現象がみられる場合に
は、金属蒸着面は不均一となり、金属光沢を有す
る部分と白化した部分とが共存することとなつ
て、光沢度の測定値には大きなバラツキがみられ
る。はじき現象のない場合には、全体的に均一な
金属光沢を有し、その測定値間にバラツキは認め
られなかつた。[Table] When a repellent phenomenon is observed in the formed coating film, the metal-deposited surface becomes uneven, and areas with metallic luster and whitened areas coexist, resulting in a change in the measured gloss value. There is a large dispersion. When there was no repelling phenomenon, the sample had uniform metallic luster as a whole, and no variation was observed between the measured values.
Claims (1)
脂水性分散液にポリビニルアルコールを全樹脂重
量の約0.03〜10％の割合で添加し、そこに形成さ
れたポリビニルアルコール混合水性分散液を紙に
塗布、乾燥させた後、その塗布面上に金属を真空
蒸着させることを特徴とする金属蒸着紙の製造方
法。 ２ ポリビニルアルコール混合水性分散液の紙へ
の塗布を複数回に分けて行なう特許請求の範囲第
１項記載の金属蒸着紙の製造方法。[Claims] 1. Polyvinyl alcohol is added to an aqueous polyolefin resin dispersion containing no surfactant at a ratio of about 0.03 to 10% of the total resin weight, and the polyvinyl alcohol mixed aqueous dispersion formed therein is A method for producing metal-deposited paper, which comprises coating the paper, drying it, and then vacuum-depositing a metal onto the coated surface. 2. The method for producing metallized paper according to claim 1, wherein the polyvinyl alcohol mixed aqueous dispersion is applied to the paper in multiple steps.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2257880A JPS56118992A (en) | 1980-02-25 | 1980-02-25 | Production of metal japor deposited paper |
| AU59616/80D AU5961680A (en) | 1979-06-29 | 1980-06-25 | Metallised paper |
| AU59616/80A AU535806B1 (en) | 1979-06-29 | 1980-06-25 | Metallised paper |
| IT8023080A IT1194667B (en) | 1979-06-29 | 1980-06-26 | PAPER ON WHICH A METAL COATING AND PROCEDURE FOR ITS PRODUCTION IS APPLIED |
| DE3024259A DE3024259C2 (en) | 1979-06-29 | 1980-06-27 | Metal coated paper and process for making the same |
| CA000355007A CA1147617A (en) | 1979-06-29 | 1980-06-27 | Metal-deposited paper and method for production thereof |
| GB8021102A GB2053283B (en) | 1979-06-29 | 1980-06-27 | Metal coated paper |
| ES492875A ES492875A0 (en) | 1979-06-29 | 1980-06-27 | A PROCEDURE FOR OBTAINING A PAPER WITH DEPOSITED METAL |
| FR8014505A FR2460780A1 (en) | 1979-06-29 | 1980-06-30 | METALLIZED PAPER COMPRISING A BONDING FILMOGEN RESIN AND PROCESS FOR PREPARING THE SAME |
| US06/619,410 US4599275A (en) | 1979-06-29 | 1984-06-13 | Metal-deposited paper and method for production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2257880A JPS56118992A (en) | 1980-02-25 | 1980-02-25 | Production of metal japor deposited paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56118992A JPS56118992A (en) | 1981-09-18 |
| JPS6221920B2 true JPS6221920B2 (en) | 1987-05-14 |
Family
ID=12086737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2257880A Granted JPS56118992A (en) | 1979-06-29 | 1980-02-25 | Production of metal japor deposited paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56118992A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5921794A (en) * | 1982-07-27 | 1984-02-03 | 三菱製紙株式会社 | Production of metal vapor deposition paper |
| AU557547B2 (en) * | 1984-08-29 | 1986-12-24 | National Starch & Chemical Corporation | Aqueous coating for meatllised paper |
| JPH03120600U (en) * | 1990-03-16 | 1991-12-11 | ||
| JP6944022B1 (en) * | 2020-07-09 | 2021-10-06 | 凸版印刷株式会社 | Gas barrier laminate and packaging bag |
| JP6944024B1 (en) * | 2020-07-09 | 2021-10-06 | 凸版印刷株式会社 | Gas barrier laminate and packaging bag |
| JP6944023B1 (en) * | 2020-07-09 | 2021-10-06 | 凸版印刷株式会社 | Gas barrier laminate and packaging bag |
| EP4209343A4 (en) * | 2020-09-30 | 2024-03-06 | Toppan Inc | Gas-barrier multilayer body and packageing bag |
| EP4209342A4 (en) * | 2020-09-30 | 2024-02-21 | Toppan Inc | Gas barrier laminate and packaging bag |
| WO2023136220A1 (en) * | 2022-01-11 | 2023-07-20 | 凸版印刷株式会社 | Gas barrier laminate and packaging bag |
-
1980
- 1980-02-25 JP JP2257880A patent/JPS56118992A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56118992A (en) | 1981-09-18 |
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