JPH0317957B2 - - Google Patents
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- Publication number
- JPH0317957B2 JPH0317957B2 JP19599585A JP19599585A JPH0317957B2 JP H0317957 B2 JPH0317957 B2 JP H0317957B2 JP 19599585 A JP19599585 A JP 19599585A JP 19599585 A JP19599585 A JP 19599585A JP H0317957 B2 JPH0317957 B2 JP H0317957B2
- Authority
- JP
- Japan
- Prior art keywords
- labels
- metal
- layer
- curing agent
- paper
- 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
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 4
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000013522 chelant Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- 239000000057 synthetic resin Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 29
- 238000001723 curing Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 239000002585 base Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical group C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 235000013405 beer Nutrition 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- -1 but in this case Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Paper (AREA)
- Laminated Bodies (AREA)
Description
（産業上の利用分野）
本発明は、酒瓶、ビール瓶等の各種の容器に貼
着するためのラベル用金属蒸着紙の製造方法に関
する。
（従来の技術）
従来、酒瓶やビール瓶等の各種の容器には、そ
の内容物、品質、ブランド等を表示するためにラ
ベル等が貼着されており、これらのラベルの基材
としては、アルミニウム箔貼合紙が広く使用され
ていたが、最近はアルミニウムを蒸着した金属蒸
着紙も広く使用されるようになつており、この金
属蒸着紙は、基材としての紙の一方の面にアンダ
ーコート層を設け、更にその上に金属蒸着層を設
け、更に必要に応じてオーバーコート層を設けて
なるものである。
このようなラベルを貼着した瓶類は、冷蔵庫等
に出し入れするために、そのラベルは十分な耐水
性が要求される。一方、これらのラベル貼着瓶類
は、その使用後再使用のために洗瓶処理される
が、その際使用するアルカリ性の洗液によつてそ
のラベルが容易に剥離されるものであることが要
求されている。
洗瓶処理時のラベルの剥離は、アルカリ洗液に
よりアルミニウム蒸着層が溶解し、次いでアンダ
ーコート層が破壊され、水が接着層に至ることに
より行われるものである。
（発明が解決しようとしている問題点）
従つて、従来は上記の如き必要条件を満足させ
るために、アルカリ可溶性のアンダーコート層を
設けることが考えられているが、この場合は、常
態における耐水性が損われるという欠点がある。
更に別の方法として、アンダーコート層中にアル
カリ可溶性の金属粉末、例えばアルミニウム粉を
含有させる方法が提案されている（例えば、特開
昭56−9776号公報）。しかしながら、この方法で
は、アルミニウム蒸着層に比して著しく多量のア
ルミニウム粉を使用するため、洗瓶処理時に多量
の水素が発生し、また洗液中に多量のアルミニウ
ムが溶解し、その廃液処理に重大な問題を生じる
ものである。
（問題点を解決するための手段）
本発明者は、上述の如き従来技術の欠点を解決
すべく鋭意研究の結果、アンダーコート剤として
特定の硬化剤を含有するものを使用し、且つ一定
の硬化条件を採用することにより、常態では優れ
た耐水性を示し、一方、洗瓶処理時には優れた剥
離性を示すラベル用金属蒸着紙が得られることを
知見して本発明を完成した。
すなわち、本発明は、基材の一面に合成樹脂よ
りなるアンダーコート層を設け、該層上に金属蒸
着層を設けてなるラベル用金属蒸着紙の製造方法
において、アンダーコート層を、硬化性被膜形成
用樹脂、金属アルコラート、金属アシラートまた
は金属のキレート化合物の硬化剤とエチレンイミ
ン系、メラミン系またはイソシアネート系の硬化
剤との混合硬化剤および媒体からなるアンダーコ
ート剤を用い、且つ該アンダーコート剤を100〜
200℃の温度で約５秒〜５分間熱硬化させる工程
で形成することを特徴とするラベル用金属蒸着紙
の製造方法である。
本発明を詳細に説明すると、本発明のラベル用
金属蒸着紙の製造方法によつてアンダーコート層
の形成に使用する硬化性被膜形成用樹脂とは、そ
の構造中に、カルボキシル基、カルボアルコキシ
基、水酸基、アミノ基、置換アミノ基、アルデヒ
ド基その他の官能基を有する樹脂であり、例えば
アクリル系、アルキド系、ブチラール系、PVA
系、PVC系、セルロース系等の従来公知の樹脂
である。
本発明で使用する硬化剤は２成分からなるもの
であるが、それらの各成分はそれぞれ単独ではい
ずれも公知の材料である。一方の成分である金属
のアルコラート、金属のアシラートまたは金属の
キレート化合物の硬化剤（以下金属系硬化剤とい
う）の金属の典型的な例は、Mg、Ca、Ba、Ｂ、
Al、Si、Sn、Ｐ、Ｓ、Ti、Zr、Fe、Co、Ni、
Cu、Zn等であり、最も有用なものはTi、Al、Sn
であり、例えばTiに関しては、Ti（OR1）４、Ti
（OR1）ｎ（OOCR2）４−ｎ、Ti（OR1）ｎ
（OR3COR4）４−ｎ等で示すことができ、更に
これらの置換基のうち、１〜２個が水素で置換さ
れたもの、あるいはそれらの金属塩も包含され
る。上記において、R1、R2、R3、R4は置換基
を有してもよいアルキル基やフエニル基等を示
す。このような金属系硬化剤は、アンダーコート
剤の媒体が水性である場合は水溶性の硬化剤を、
媒体が油性である場合は油溶性の硬化剤を使用す
るのが好ましい。
上記の金属系硬化剤は、硬化性被膜形成用樹脂
（固形分）100重量部あたり、約１〜20重量部の割
合で使用する。
本発明で使用する硬化剤の他方の成分であるエ
チレンイミン系、メラミン系またはイソシアネー
ト系の硬化剤（以下アミン系硬化剤という）は、
それ自体公知でいずれも工業的に入手し得るもの
である。このようなアミン系硬化剤は、前記の硬
化性被膜形成用樹脂100重量部あたり約１〜30重
量部の割合、および前記の金属系硬化剤100重量
部あたり約40〜200重量部の割合で使用するのが
好ましい。
本発明で使用する媒体は、水、メタノール、エ
タノール、イソプロピルアルコール、酢酸エチ
ル、メチルエチルケトン、セロソルブアセテー
ト、エチルセロソルブ、トルエンその他の溶剤の
単独あるいは混合物であり、硬化性被膜形成用樹
脂その他の成分からなる固形分が約10〜70重量部
％になる割合で使用する。
本発明のラベル用金属蒸着紙の製造方法におい
て使用するアンダーコート剤は、上記の必須成分
を適当な任意の手段で混合することにより調製で
きるが、その際の各種の添加剤等を必要に応じて
添加することができる。
上記の構成からなるアンダーコート剤は、任意
の基体面に塗布し、適当な時間（例えば１分間以
内）、適当な温度（例えば100〜200℃）で乾燥す
ると、常態では強靭で表面平滑な被膜を形成す
る。この被膜は優れた耐水性を有する一方で、ア
ルカリ性の媒体に対しては速やかに劣化し、透水
性になり、場合によつては剥離するものである。
本発明のラベル用金属蒸着紙の製造方法は、上
記アンダーコート剤を用い、且つ一定の硬化条件
でアンダーコート層を設けたことを特徴とし、該
層上に金属蒸着紙を設け、必要に応じて更にオー
バーコート層を設けてなるものである。以下、本
発明の方法を図面を参照して具体的に説明する。
図面は本発明により製造されるラベル用金属蒸
着紙の一例を図解的に示す一部拡大断面図であ
り、１は紙、コート紙等の基材を表わし、２はア
ンダーコート層であり、３は金属蒸着層であり、
４は必要に応じて設けるオーバーコート層であ
る。基材１は従来公知のラベル用の基材がそのま
ま使用でき、アンダーコート層２は、前記の被膜
形成剤を、グラビアコート法、ロールコート法、
エアナイフ法等の如き方法により、約１〜20ミク
ロン（乾燥時）の厚さに塗布し、次いで約100〜
200℃の温度で約５秒〜５分間熱硬化させること
により容易に形成される。次いで、通常の方法で
アルミニウム、亜鉛、鉄、クロム等の金属を真空
蒸着して蒸着層３を形成させる。
更に必要に応じて、アクリル系、環化ゴム系、
塩化ゴム系、セルロース系誘導体、マレイン酸樹
脂、アルキツド樹脂、スチレン−マレイン酸樹脂
等によりオーバーコート層４を設けることにより
本発明により製造されるラベル用金属蒸着紙が得
られる。このような本発明により製造されるラベ
ル用金属蒸着紙を、アルカリ剥離性の接着剤によ
り各種の瓶類に貼着したものは、湿気の強い雰囲
気は勿論のこと、水中においてもそのアンダーコ
ート層がクラツクを生じることなく、十分な耐水
性を示し、水を通さないので十分な耐剥離性を示
し、一方、洗瓶工程時のアルカリ性の洗液によつ
て、まず表面の蒸着層が溶解し、次いでアンダー
コート層も速やかに劣化して透水性になるので、
アルカリ性の洗液が直ちに接着層に達し、ラベル
の剥離が容易に達成される。
以上の如き本発明により製造されるラベル用金
属蒸着紙は、その洗瓶処理時に水素ガスの発生が
極めて少なく、またアルカリ洗液中に溶解するア
ルミニウム等はその蒸着層の金属のみであるか
ら、このような点からも非常に有用である。
次に実施例を挙げて本発明を更に具体的に説明
する。なお、文中、部または％とあるのは重量基
準である。
実施例
下記第１表に記載の成分を混合し、本発明で使
用する各種のアンダーコート剤を調製し、得られ
たアンダーコート剤を基材（紙）上に５ｇ／m2〜
20ｇ／m2の量で塗布し、110℃〜180℃で５〜120
秒間硬化させ、次いでその表面にアルミニウムを
蒸着してラベル用金属蒸着紙を得、この金属蒸着
紙について各種の試験を行つた。その結果を第２
表に示す。各種の試験の試験条件は下記の通りで
ある。
１ 蒸着適性試験；接着性試験はセロテープ剥離
テストで行い、光沢は目視で行い、耐熱性は
120℃×10秒で焼けの有無により判定し、良ま
たは不良で表示した。
２ 耐水性；室温で24時間水中に浸漬し、アルミ
ニウム表面の白化および表面クラツキングの有
無を調べ、良または不良で表示した。
３ アルカリ適性；ガラス板上に貼着し乾燥した
金属蒸着紙を、60〜70℃に加温した３％の苛性
ソーダ水溶液に浸漬し、ラベルが剥離する時間
を測定した。
下記第１〜２表中におけるNo.１〜13は本発明の
実施例であり、No.14〜17は比較例である。第１表
中の金属系硬化剤のR1は−CH3、−C2H5または
−C3H7であり、R2はCH3CH＝またはCH3CH
＝CH−であり、R3は−CH3、−OCH3、または
−OC2H5である。またエチレンイミン系硬化剤
のR1は−Ｈ、−CH3または−C2H5であり、R2は
−OH、
(Industrial Application Field) The present invention relates to a method for producing metallized paper for labels to be attached to various containers such as liquor bottles and beer bottles. (Prior Art) Conventionally, various containers such as liquor bottles and beer bottles have labels attached to them to indicate their contents, quality, brand, etc. The base materials for these labels include: Aluminum foil-laminated paper was widely used, but recently metallized paper with aluminum vapor-deposited has also become widely used. A coat layer is provided, a metal vapor deposition layer is further provided thereon, and an overcoat layer is further provided as necessary. Bottles with such labels attached thereto are required to have sufficient water resistance in order to be taken out and put into refrigerators and the like. On the other hand, these labeled bottles are washed for reuse after use, but the labels may be easily peeled off by the alkaline washing liquid used at that time. requested. Peeling of the label during bottle washing is performed by dissolving the aluminum deposited layer with the alkaline washing solution, then destroying the undercoat layer, and allowing water to reach the adhesive layer. (Problems to be Solved by the Invention) Therefore, in order to satisfy the above-mentioned requirements, it has conventionally been considered to provide an alkali-soluble undercoat layer, but in this case, water resistance under normal conditions The disadvantage is that it is damaged.
As yet another method, a method has been proposed in which an alkali-soluble metal powder, such as aluminum powder, is contained in the undercoat layer (for example, Japanese Patent Application Laid-Open No. 1987-9776). However, since this method uses a significantly larger amount of aluminum powder than the aluminum vapor deposited layer, a large amount of hydrogen is generated during bottle washing, and a large amount of aluminum is dissolved in the washing liquid, resulting in the waste liquid being disposed of. This poses serious problems. (Means for Solving the Problems) As a result of intensive research to solve the above-mentioned drawbacks of the prior art, the present inventor used an undercoat agent containing a specific curing agent and The present invention was completed based on the finding that by employing curing conditions, it is possible to obtain a metal-deposited paper for labels that exhibits excellent water resistance under normal conditions and exhibits excellent releasability during bottle washing treatment. That is, the present invention provides a method for producing metal-deposited paper for labels, in which an undercoat layer made of a synthetic resin is provided on one side of a base material, and a metal-deposited layer is provided on the layer. Using an undercoat agent consisting of a mixed curing agent of a forming resin, a metal alcoholate, a metal acylate, or a metal chelate compound curing agent and an ethyleneimine-based, melamine-based, or isocyanate-based curing agent, and a medium; 100～
This is a method for producing metallized paper for labels, characterized in that the metallized paper for labels is formed by a step of heat curing at a temperature of 200° C. for about 5 seconds to 5 minutes. To explain the present invention in detail, the curable film-forming resin used for forming the undercoat layer in the method for producing metallized paper for labels of the present invention has carboxyl groups and carbalkoxy groups in its structure. , hydroxyl group, amino group, substituted amino group, aldehyde group, and other functional groups, such as acrylic, alkyd, butyral, and PVA.
These are conventionally known resins such as PVC-based, PVC-based, cellulose-based, etc. The curing agent used in the present invention consists of two components, and each of these components alone is a known material. Typical examples of metals in the curing agent for metal alcoholate, metal acylate, or metal chelate compound (hereinafter referred to as metal curing agent) that are one of the components include Mg, Ca, Ba, B,
Al, Si, Sn, P, S, Ti, Zr, Fe, Co, Ni,
Cu, Zn, etc., and the most useful ones are Ti, Al, Sn
For example, for Ti, Ti(OR1)4, Ti
(OR1)n(OOCR2)4-n, Ti(OR1)n
(OR3COR4)4-n, etc., and further includes those in which one or two of these substituents are substituted with hydrogen, or metal salts thereof. In the above, R1, R2, R3, and R4 represent an alkyl group, a phenyl group, etc. which may have a substituent. If the medium of the undercoat agent is water-based, such metal-based hardeners may be mixed with water-soluble hardeners,
When the medium is oil-based, it is preferable to use an oil-soluble curing agent. The above metal curing agent is used in an amount of about 1 to 20 parts by weight per 100 parts by weight of the curable film-forming resin (solid content). The other component of the curing agent used in the present invention, an ethyleneimine-based, melamine-based or isocyanate-based curing agent (hereinafter referred to as an amine-based curing agent), is
All of them are known per se and can be obtained industrially. The amine curing agent is used in an amount of about 1 to 30 parts by weight per 100 parts by weight of the curable film-forming resin, and about 40 to 200 parts by weight per 100 parts by weight of the metal curing agent. It is preferable to use The medium used in the present invention is water, methanol, ethanol, isopropyl alcohol, ethyl acetate, methyl ethyl ketone, cellosolve acetate, ethyl cellosolve, toluene, and other solvents, singly or in mixtures, and consists of a curable film-forming resin and other components. It is used in a proportion where the solid content is about 10 to 70 parts by weight. The undercoat agent used in the method for producing metallized paper for labels of the present invention can be prepared by mixing the above-mentioned essential components by any appropriate means, and various additives may be added as necessary. can be added. When the undercoat agent having the above structure is applied to any substrate surface and dried at an appropriate temperature (e.g. 100 to 200°C) for an appropriate time (e.g. within 1 minute), it normally forms a tough coating with a smooth surface. form. While this coating has excellent water resistance, it quickly deteriorates in alkaline media, becomes water permeable, and in some cases peels off. The method for producing metallized paper for labels of the present invention is characterized in that an undercoat layer is provided using the above-mentioned undercoat agent and under certain curing conditions, and metallized paper is provided on the layer, and if necessary, the undercoat layer is provided. Furthermore, an overcoat layer is provided. Hereinafter, the method of the present invention will be specifically explained with reference to the drawings. The drawing is a partially enlarged sectional view schematically showing an example of metallized paper for labels produced according to the present invention, in which 1 represents a base material such as paper or coated paper, 2 represents an undercoat layer, and 3 is a metal deposited layer,
4 is an overcoat layer provided as necessary. For the base material 1, a conventionally known base material for labels can be used as is, and for the undercoat layer 2, the above-mentioned film forming agent is applied by gravure coating, roll coating,
Apply to a thickness of about 1 to 20 microns (when dry) by a method such as the air knife method, then apply to a thickness of about 100 to 20 microns (when dry).
It is easily formed by heat curing at a temperature of 200°C for about 5 seconds to 5 minutes. Next, a metal such as aluminum, zinc, iron, chromium, etc. is vacuum-deposited using a conventional method to form a deposited layer 3. Furthermore, if necessary, acrylic, cyclized rubber,
By providing an overcoat layer 4 of chlorinated rubber, cellulose derivative, maleic resin, alkyd resin, styrene-maleic resin, etc., the metallized paper for labels produced according to the present invention can be obtained. When the metallized paper for labels produced according to the present invention is attached to various types of bottles using an alkaline removable adhesive, the undercoat layer can be easily removed not only in a humid atmosphere but also in water. It shows sufficient water resistance without causing cracks, and shows sufficient peeling resistance because it does not allow water to pass through.On the other hand, the vapor deposited layer on the surface is first dissolved by the alkaline washing liquid during the bottle washing process. Then, the undercoat layer also quickly deteriorates and becomes water permeable.
The alkaline washing liquid reaches the adhesive layer immediately and peeling of the label is easily achieved. The metal-deposited paper for labels manufactured according to the present invention as described above generates very little hydrogen gas during the bottle washing process, and the only metal such as aluminum that dissolves in the alkaline washing solution is the metal in the vapor-deposited layer. It is also very useful from this point of view. Next, the present invention will be explained in more detail with reference to Examples. Note that parts and percentages in the text are based on weight. Examples Various undercoating agents used in the present invention were prepared by mixing the components listed in Table 1 below, and the obtained undercoating agents were applied onto a substrate (paper) at a rate of 5 g/m 2 to
Apply in an amount of 20g/ m2 , 5 to 120 at 110℃ to 180℃
After curing for seconds, aluminum was then deposited on the surface to obtain metallized paper for labels, and various tests were conducted on this metallized paper. The second result is
Shown in the table. The test conditions for the various tests are as follows. 1 Vapor deposition aptitude test: Adhesion test was performed using cellophane tape peeling test, gloss was checked visually, and heat resistance was determined by visual inspection.
Judgment was made based on the presence or absence of burns at 120°C for 10 seconds, and the results were marked as good or bad. 2. Water resistance: It was immersed in water at room temperature for 24 hours, and the presence or absence of whitening and surface cracking on the aluminum surface was examined and rated as good or bad. 3 Alkali suitability: A metallized paper that had been adhered to a glass plate and dried was immersed in a 3% caustic soda aqueous solution heated to 60 to 70°C, and the time it took for the label to peel off was measured. In Tables 1 and 2 below, Nos. 1 to 13 are examples of the present invention, and Nos. 14 to 17 are comparative examples. R1 of the metallic curing agent in Table 1 is -CH3, -C2H5 or -C3H7, and R2 is CH3CH= or CH3CH
=CH-, and R3 is -CH3, -OCH3, or -OC2H5. In addition, R1 of the ethyleneimine curing agent is -H, -CH3 or -C2H5, and R2 is -OH,
【式】または−COORであり、R3は− Ｈ、[Formula] or −COOR, and R3 is − H,
【式】または[expression] or
【式】である。
下記第２表から明らかな通り、本発明により製
造されるラベル用金属蒸着紙は優れた耐水性とと
もに、優れたアルカリ適性を有する被膜を形成す
るものである。[Formula]. As is clear from Table 2 below, the metallized paper for labels manufactured according to the present invention forms a film having excellent water resistance and excellent alkali suitability.
【表】【table】
【表】【table】
【表】【table】
図面は本発明の使用例のラベル用金属蒸着紙の
１例を示す一部拡大断面図であり、図中１は基
材、２はアンダーコート層、３は金属蒸着層、４
はオーバーコート層を示す。
The drawing is a partially enlarged cross-sectional view showing an example of metallized paper for labels according to the present invention, in which 1 is a base material, 2 is an undercoat layer, 3 is a metallized layer, and 4 is a metallized metallized paper for labels.
indicates an overcoat layer.
Claims (1)
ト層を設け、該層上に金属蒸着層を設けてなるラ
ベル用金属蒸着紙の製造方法において、アンダー
コート層を、硬化性被膜形成用樹脂、金属アルコ
ラート、金属アシラートまたは金属のキレート化
合物の硬化剤とエチレンイミン系、メラミン系ま
たはイソシアネート系の硬化剤との混合硬化剤お
よび媒体からなるアンダーコート剤を用い、且つ
該アンダーコート剤を100〜200℃の温度で約５秒
〜５分間熱硬化させる工程で形成することを特徴
とするラベル用金属蒸着紙の製造方法。1. In a method for producing metallized paper for labels, in which an undercoat layer made of a synthetic resin is provided on one side of a base material, and a metallized layer is provided on the layer, the undercoat layer is formed of a curable film-forming resin, a metal An undercoating agent consisting of a mixed curing agent of an alcoholate, metal acylate, or metal chelate compound curing agent and an ethyleneimine-based, melamine-based, or isocyanate-based curing agent and a medium is used, and the undercoating agent is heated at 100 to 200°C. 1. A method for producing metallized paper for labels, comprising a step of thermally curing the paper at a temperature of about 5 seconds to 5 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19599585A JPS6175376A (en) | 1985-09-06 | 1985-09-06 | Metal evaporation paper for label |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19599585A JPS6175376A (en) | 1985-09-06 | 1985-09-06 | Metal evaporation paper for label |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6175376A JPS6175376A (en) | 1986-04-17 |
| JPH0317957B2 true JPH0317957B2 (en) | 1991-03-11 |
Family
ID=16350469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19599585A Granted JPS6175376A (en) | 1985-09-06 | 1985-09-06 | Metal evaporation paper for label |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6175376A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2441376A1 (en) | 2010-10-12 | 2012-04-18 | Fujifilm Corporation | Switching valve assembly for endoscope |
| EP2441377A1 (en) | 2010-10-12 | 2012-04-18 | Fujifilm Corporation | Switching valve assembly for endoscope |
| EP2441379A1 (en) | 2010-10-12 | 2012-04-18 | Fujifilm Corporation | Switching valve assembly for endoscope |
| EP2878252A1 (en) | 2013-11-28 | 2015-06-03 | Fujifilm Corporation | Switching valve unit and endoscope apparatus |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5052742A (en) * | 1989-06-30 | 1991-10-01 | Toyota Jidosha Kabushiki Kaisha | Cowlside joint structure for use with vehicle |
-
1985
- 1985-09-06 JP JP19599585A patent/JPS6175376A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2441376A1 (en) | 2010-10-12 | 2012-04-18 | Fujifilm Corporation | Switching valve assembly for endoscope |
| EP2441377A1 (en) | 2010-10-12 | 2012-04-18 | Fujifilm Corporation | Switching valve assembly for endoscope |
| EP2441379A1 (en) | 2010-10-12 | 2012-04-18 | Fujifilm Corporation | Switching valve assembly for endoscope |
| EP2878252A1 (en) | 2013-11-28 | 2015-06-03 | Fujifilm Corporation | Switching valve unit and endoscope apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6175376A (en) | 1986-04-17 |
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