JPH0732718A - Transfer foil for vinyl chloride resin base material - Google Patents
Transfer foil for vinyl chloride resin base materialInfo
- Publication number
- JPH0732718A JPH0732718A JP5198822A JP19882293A JPH0732718A JP H0732718 A JPH0732718 A JP H0732718A JP 5198822 A JP5198822 A JP 5198822A JP 19882293 A JP19882293 A JP 19882293A JP H0732718 A JPH0732718 A JP H0732718A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- vinyl chloride
- layer
- transfer foil
- base material
- 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.)
- Pending
Links
Landscapes
- Printing Methods (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、塩化ビニル系樹脂から
なる基材の表面を化粧するための塩化ビニル系樹脂基材
用転写箔に関し、特に塩化ビニル樹脂成形体表面を化粧
し、外装用途や水回り用途などの耐候性、耐摩性、耐熱
水性が要求される用途に好適の化粧材を提供できる転写
箔に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer foil for a vinyl chloride resin base material for making up the surface of a base material made of vinyl chloride resin. The present invention relates to a transfer foil capable of providing a decorative material suitable for applications requiring weather resistance, abrasion resistance, and hot water resistance such as water and water applications.
【０００２】[0002]
【従来の技術】従来、塩化ビニル系樹脂の成形体を用い
た外装材あるいは内装材において、樹脂の成形体のまま
では意匠性に乏しいために、樹脂成形体の表面に種々の
方法で模様付けを行い、意匠感の有る内外装材としてい
る。例えば、塩化ビニル樹脂の押し出し成形体にあって
は、その表面にグラビアオフセット印刷、シルクスクリ
ーン印刷その他の印刷方法によって直接絵柄を形成し、
さらにその上に透明なクリヤー保護層を形成して仕上げ
る方法がある。あるいは、樹脂成形体を形成する樹脂そ
のものの中に着色顔料やパール顔料等を混入した樹脂原
料を用いて成形した樹脂成形体とし、それで最終的な内
外装材とする方法等もあった。さらに、樹脂成形体の表
面への絵柄の形成を間接的に、すなわち転写箔により形
成する方法も試みられていた。2. Description of the Related Art Conventionally, in an exterior material or an interior material using a molded product of vinyl chloride resin, the resin molded product is poor in design, and therefore, the surface of the resin molded product is patterned by various methods. The interior and exterior materials have a design feeling. For example, in the case of an extrusion molded body of vinyl chloride resin, a pattern is directly formed on its surface by gravure offset printing, silk screen printing or other printing method,
Further, there is a method of forming a transparent clear protective layer on it and finishing. Alternatively, there is also a method of forming a resin molded body by using a resin raw material in which a color pigment, a pearl pigment, or the like is mixed in the resin itself forming the resin molded body, and using it as a final interior / exterior material. Furthermore, a method of indirectly forming a pattern on the surface of the resin molded body, that is, a method of forming the pattern with a transfer foil has been attempted.
【０００３】[0003]
【発明が解決しようとする課題】しかし、従来の塩化ビ
ニル系樹脂成形体からなる意匠性を有する内外装材の製
造において、上記した直接に絵柄を樹脂成形体の表面に
グラビア、オフセット印刷、その他の印刷方法によって
形成する方法の場合、被印刷面となる樹脂成形体の表面
は厚みが厚い上に平滑性が悪かったり、あるいは、平面
であることは通常稀であり、また、それら平面の組み合
わせからなる樹脂成形体に対しては、各々の平面毎に印
刷を繰り返す必要があった。この為に、複数の面毎に絵
柄を印刷する場合には絵柄の見当合わせが困難であり、
さらに多色刷りにおいては絵柄が不鮮明となり、意匠感
に優れた外装材とすることは困難であった。しかも、一
色の印刷毎に乾燥工程が必要となるために、多色印刷の
場合には極めて生産効率が悪かった。くわえて、印刷形
成された絵柄を保護する意味で、透明なクリヤー保護層
を印刷後に別途形成するための後工程も必要であるな
ど、得られる意匠感の割りにコスト高となるものであっ
た。However, in the production of conventional interior / exterior material made of vinyl chloride resin moldings, the above-mentioned direct pattern is directly applied to the surface of the resin molding by gravure, offset printing, etc. In the case of the method of forming by the printing method described above, the surface of the resin molded body to be printed has a large thickness and poor smoothness, or is rarely a plane, and a combination of these planes is also rare. It was necessary to repeat printing on each of the flat surfaces of the resin molded body made of. For this reason, it is difficult to register the pattern when printing the pattern on each of a plurality of surfaces.
Further, in multicolor printing, the pattern becomes unclear, and it is difficult to make the exterior material excellent in design. Moreover, since a drying step is required for each one-color printing, the production efficiency was extremely poor in the case of multicolor printing. In addition, in order to protect the pattern formed by printing, a post process for separately forming a transparent clear protective layer after printing is required, and the cost is high relative to the obtained design feeling. .
【０００４】また、樹脂成形体を形成する樹脂原料に、
着色顔料やパール顔料を混入したものを用いて内外装材
を製造する場合には、柄模様の意匠を表現することが本
質的に不可能であり、原料樹脂に前記顔料を混ぜ合わせ
る工程が必要になる反面、極めて単調な意匠感を有する
内外装材しか得られなかった。Further, as a resin raw material for forming a resin molding,
When manufacturing an interior / exterior material using a mixture of a coloring pigment or a pearl pigment, it is essentially impossible to express the design of the pattern, and a step of mixing the pigment with the raw material resin is required. However, only the interior / exterior material having a very monotonous design feeling was obtained.
【０００５】さらに、樹脂成形体に間接的に、すなわち
転写法によって、一旦印刷適性の良い薄い平滑な基材フ
ィルム上に印刷形成した絵柄を成形体表面に転移させて
化粧する試みもなされて来てはいるが、押し出し成形体
のような表面が平滑でない基材に対しては、均一に転写
することが難しく、また室内用途の化粧材と違い雨風や
直射日光等の厳しい条件にに曝される外装用途、あるい
は、浴室、キッチンなどの水回りに使用される内装用途
においては、基本的な転写性能を具備しつつ、耐候性、
耐摩性、耐熱水性等の点でも充分に満足できる特性を具
備した実用的な転写箔は得られていなかった。特に、外
装用、浴室用では、煮沸水に浸漬して加熱する試験を行
っても、変色、層間剥離を起こさないことが要求され
る。現在、業界では、一番厳しい規格としては、最大１
０時間煮沸に耐えることが要求される。また、外装用に
於いては、耐候性として、カーボンアーク燈サンシャイ
ンウエザオメータ（耐候性促進試験機）で最低１０００
時間照射しても、変褪色、転写層の剥脱等のないことが
要求される。Further, it has been attempted to indirectly apply a makeup to a resin molded product, that is, by a transfer method, to transfer a pattern once printed and formed on a thin smooth base film having good printability to the surface of the molded product to make up. However, it is difficult to transfer uniformly to a substrate such as an extruded body with a non-smooth surface, and unlike a decorative material for indoor use, it is exposed to severe conditions such as rain wind and direct sunlight. For exterior applications such as that used for interior or interior applications used around bathrooms, kitchens, etc., while having basic transfer performance, weather resistance,
A practical transfer foil having sufficiently satisfactory properties in terms of abrasion resistance and hot water resistance has not been obtained. In particular, for exteriors and bathrooms, it is required that discoloration or delamination does not occur even when a test of immersing in boiling water and heating is performed. Currently, the strictest standard in the industry is 1
It is required to withstand boiling for 0 hours. For exterior use, the weather resistance of carbon arc lamp sunshine weatherometer (weather resistance tester) should be at least 1000.
It is required that even after irradiation for a long time, there is no discoloration or peeling of the transfer layer.
【０００６】そこで、本発明は、特に塩化ビニル系樹脂
基材用途の転写箔において、耐候性、耐摩性、耐熱水性
が優れた塩化ビニル系樹脂基材用転写箔を提供すること
を目的としている。[0006] Therefore, an object of the present invention is to provide a transfer foil for vinyl chloride resin base material, which is excellent in weather resistance, abrasion resistance and hot water resistance, especially in transfer foil for vinyl chloride resin base material. .
【０００７】[0007]
【課題を解決するための手段】そこで、本発明では上記
課題を解決するために、転写箔用基材の一方の面に、ア
クリル系樹脂又は塩化ビニル・酢酸ビニル共重合体樹脂
とアクリル系樹脂との混合樹脂にワックス又は／及び減
摩剤を添加した剥離層と、アクリル系樹脂をビヒクルの
主体とする印刷層による装飾層と、塩化ビニル・酢酸ビ
ニル共重合体樹脂からなる接着剤層とが順次積層されて
いることを特徴とした塩化ビニル系樹脂基材用転写箔と
するものである。また、前記接着剤層を構成する塩化ビ
ニル・酢酸ビニル共重合体樹脂の二次転移温度（Ｔｇ）
が１００〜１１０℃で、且つ平均分子量が６００００〜
８００００であることを特徴とした塩化ビニル系樹脂基
材用転写箔とするものである。In order to solve the above-mentioned problems, the present invention provides an acrylic resin or a vinyl chloride / vinyl acetate copolymer resin and an acrylic resin on one surface of a transfer foil substrate. A release layer in which wax or / and an anti-friction agent is added to a mixed resin with, a decorative layer formed by a printing layer mainly composed of an acrylic resin as a vehicle, and an adhesive layer made of a vinyl chloride / vinyl acetate copolymer resin Is sequentially laminated, which is a transfer foil for vinyl chloride resin base material. The second-order transition temperature (Tg) of the vinyl chloride / vinyl acetate copolymer resin forming the adhesive layer
Is 100 to 110 ° C., and the average molecular weight is 60,000 to
The transfer foil for vinyl chloride resin base material is characterized in that it is 80,000.
【０００８】以下、図面に従って本発明を詳述する。図
１は本発明に係わる一実施例を示す塩化ビニル系樹脂基
材用転写箔の縦断面図である。本発明による塩化ビニル
系樹脂基材用転写箔１は、転写箔用基材２の片面に、剥
離層３、装飾層４、接着剤層５を順次設けた構成からな
る。転写の際は、転写箔用基材２と剥離層３との界面で
剥離し被転写基材側に転写される層、すなわち転写層６
は、転写後の状態で表層から順次剥離層３、装飾層４、
接着剤層５となる。The present invention will be described in detail below with reference to the drawings. FIG. 1 is a vertical cross-sectional view of a transfer foil for vinyl chloride resin base material showing an embodiment according to the present invention. The transfer foil 1 for vinyl chloride resin base material according to the present invention has a structure in which a release layer 3, a decorative layer 4, and an adhesive layer 5 are sequentially provided on one surface of a transfer foil base material 2. At the time of transfer, a layer that is peeled off at the interface between the transfer foil substrate 2 and the peeling layer 3 and is transferred to the substrate to be transferred, that is, the transfer layer 6
Is a peeling layer 3, a decorative layer 4, and the like in order from the surface layer after the transfer.
It becomes the adhesive layer 5.
【０００９】転写箔用基材２は、剥離層３との剥離性の
よいものが利用され、例えば、ポリエチレンテレフタレ
ート、ポリエチレンテレフタレート・イソフタレートコ
ポリマー、ポリブチレンテレフタレート等のポリエステ
ルフィルム、ポリプロピレン等のポリオレフィンフィル
ム等が利用でき、特に厚さ１０〜１００μｍの２軸延伸
ポリエチレンテレフタレートフィルム、ポリプロピレン
等のポリオレフィンを上質紙等に塗工した塗工紙等が好
適である。なお、剥離層３との剥離性を制御する意味
で、図示はしないが転写箔用基材２の剥離層３が形成さ
れる面に離型層を設けたものであってもよい。離型層
は、フッ素系樹脂、各種ワックス、シリコーン等の離型
剤を公知のビヒクル、例えば、アクリル系樹脂、セルロ
ース系樹脂、ビニル系樹脂等に添加した塗料の塗膜を形
成したり、離型性の樹脂、例えば、フッ素系樹脂、シリ
コーン、メラミン系樹脂、ポリオレフィン系樹脂、電離
放射線硬化性アクリル系樹脂等を塗工、あるいはエクス
トルージョンコート等で製膜したものを用いればよい。As the transfer foil substrate 2, a material having good releasability from the release layer 3 is used, and examples thereof include polyester films such as polyethylene terephthalate, polyethylene terephthalate / isophthalate copolymer, polybutylene terephthalate, and polyolefin films such as polypropylene. And the like, and in particular, a biaxially stretched polyethylene terephthalate film having a thickness of 10 to 100 μm, a coated paper obtained by coating a polyolefin such as polypropylene on a high quality paper, and the like are preferable. In order to control the releasability from the release layer 3, a release layer may be provided on the surface of the transfer foil substrate 2 on which the release layer 3 is formed, although not shown. The release layer forms a coating film of a paint in which a release agent such as a fluororesin, various waxes and silicones is added to a known vehicle such as an acrylic resin, a cellulose resin, a vinyl resin, or a release agent. A moldable resin, for example, a fluorine resin, silicone, melamine resin, polyolefin resin, ionizing radiation curable acrylic resin, or the like may be applied, or a film formed by extrusion coating or the like may be used.
【００１０】剥離層３は、転写箔から装飾層が被転写基
材に転写された以降、転写層６の最外層となるものであ
り、装飾層４の上層となって装飾層４を保護する役割を
果たし、本願目的の一つである優れた耐摩性を具現化す
る際に特に重要な構成要素である。優れた耐候性に顕著
な効果を奏する剥離層３としては、アクリル系樹脂が最
適であるが、アクリル系樹脂単体だと塗膜が硬すぎて、
転写時或いは、転写後の温度変化、外力等により亀裂が
入るという欠点がある。これを改善する為に、塩化ビニ
ル・酢酸ビニル共重合体樹脂をアクリル系樹脂に混合す
る。混合比は、アクリル系樹脂／塩化ビニル・酢酸ビニ
ル共重合体樹脂＝９／１〜７／３の範囲であり、特に８
／２程度が好ましい。アクリル系樹脂が少ないと耐候性
が低下し、日光暴露によって黄変等を生じやすくなる。
また、アクリル系樹脂としては、例えばポリメタクリル
酸メチル、ポリメタクリル酸エチル、ポリメタクリル酸
ブチル、ポリメタクリル酸エチルヘキシル等のメタクリ
ル酸アルキルエステル単独重合体、ポリアクリル酸メチ
ル、ポリアクリル酸エチル、ポリアクリル酸ブチル、ポ
リアクリル酸エチルヘキシル等のアクリル酸アルキルエ
ステル単独重合体、該アクリル酸アルキルエステルやメ
タクリル酸アルキルエステル同士の共重合体、あるいは
該アクリル酸アルキルエステル、メタクリル酸アルキル
エステルと塩化ビニル、酢酸ビニル等との共重合体等の
樹脂が好ましい。The peeling layer 3 serves as the outermost layer of the transfer layer 6 after the decorative layer is transferred from the transfer foil to the transferred substrate and protects the decorative layer 4 as an upper layer of the decorative layer 4. It plays a role and is a particularly important constituent element when realizing excellent wear resistance, which is one of the purposes of the present application. Acrylic resin is the most suitable as the release layer 3 which has a remarkable effect on excellent weather resistance, but when the acrylic resin is used alone, the coating film is too hard,
There is a drawback in that cracks may occur during transfer or after transfer due to temperature changes, external forces, and the like. In order to improve this, a vinyl chloride / vinyl acetate copolymer resin is mixed with an acrylic resin. The mixing ratio is acrylic resin / vinyl chloride / vinyl acetate copolymer resin = 9/1 to 7/3, particularly 8
About / 2 is preferable. When the amount of the acrylic resin is small, the weather resistance is deteriorated, and yellowing is likely to occur due to exposure to sunlight.
Examples of the acrylic resin include homopolymers of alkyl methacrylates such as polymethylmethacrylate, polyethylmethacrylate, polybutylmethacrylate, and polyethylhexylmethacrylate, poly (methyl acrylate), poly (ethyl acrylate), poly (acrylic acid). Acrylic acid alkyl ester homopolymers such as butyl acrylate and poly (ethylhexyl acrylate), copolymers of the acrylic acid alkyl ester and methacrylic acid alkyl ester, or the acrylic acid alkyl ester, methacrylic acid alkyl ester and vinyl chloride, vinyl acetate Resins such as copolymers with the above are preferable.
【００１１】上記、アクリル系樹脂、又は塩化ビニル・
酢酸ビニル共重合体樹脂とアクリル系樹脂との混合樹脂
に対して添加することにより、顕著な耐摩性の向上効果
を奏するワックス、減摩剤であるが、このようなワック
スとしては、例えば、ポリエチレン系ワックス、フッ素
樹脂系ワックス、パラフィン、蝋等が挙げられ、添加量
は樹脂全量に対して０．１〜５重量％が好ましい。ま
た、減摩剤としてはアルミナ、炭化珪素、シリカ等の鉱
物系微粉末が挙げられ、添加量としては樹脂全量に対し
て、０．１〜２重量％が好ましい。添加量が少なすぎる
と、耐摩性の向上効果が得られず、逆に多すぎると、剥
離層と装飾層の密着性が低下したり、あるい減摩剤の量
が多すぎると、減摩剤が離型層表面に露出し表面平滑な
転写層の用途に向かない。The above-mentioned acrylic resin or vinyl chloride
Waxes and antifriction agents that have a remarkable effect of improving the wear resistance when added to a mixed resin of a vinyl acetate copolymer resin and an acrylic resin. Examples of such a wax include polyethylene. System wax, fluororesin wax, paraffin, wax and the like can be mentioned, and the addition amount is preferably 0.1 to 5% by weight with respect to the total amount of the resin. Further, examples of the lubricant include fine powders of minerals such as alumina, silicon carbide and silica, and the addition amount is preferably 0.1 to 2% by weight based on the total amount of the resin. If the amount added is too small, the effect of improving the wear resistance cannot be obtained, and conversely, if it is too large, the adhesion between the release layer and the decorative layer decreases, or if the amount of the lubricant is too large, the wear resistance decreases. The agent is exposed on the surface of the release layer and is not suitable for use as a transfer layer having a smooth surface.
【００１２】剥離層３には、紫外線による劣化を防止す
る意味で、光安定剤が必要に応じて添加される。例え
ば、２−（２′−ヒドロキシ−３′，５′−ジ−ｔｅｒ
ｔ−ブチルフェニル）−５−クロロベンゾトリアゾー
ル、２−（２′−ヒドロキシ−３′−ｔｅｒｔ−ブチル
−５′−メチルフェニル）−５−クロロベンゾトリアゾ
ール、２−（２′−ヒドロキシ−３′−ｔｅｒｔ−アミ
ル−５′−イソブチルフェニル）−５−クロロベンゾト
リアゾール、２−（２′−ヒドロキシ−３′−イソブチ
ル−５′−メチルフェニル）−５−クロロベンゾトリア
ゾール、２−（２′−ヒドロキシ−３′−イソブチル−
５′−プロピルフェニル）−５−クロロベンゾトリアゾ
ール等の２′−ヒドロキシフェニル−５−クロロベンゾ
トリアゾール系紫外線吸収剤類、２−（２′−ヒドロキ
シ−３′，５′−ジ−ｔｅｒｔ−ブチルフェニル）ベン
ゾトリアゾール、２−（２′−ヒドロキシ−５′−メチ
ルフェニル）ベンゾトリアゾール等の２′−ヒドロキシ
フェニルベンゾトリアゾール系紫外線吸収剤類、２，
２′−ジヒドロキシ−４−メトキシベンゾフェノン、
２，２′−ジヒドロキシ−４，４′−ジメトキシベンゾ
フェノン、２，２′，４，４′−テトラヒドロキシベン
ゾフェノン等の２，２′−ジヒドロキシベンゾフェノン
系紫外線吸収剤類、２−ヒドロキシ−４−メトキシベン
ゾフェノン、２，４−ジヒドロキシベンゾフェノン等の
２−ヒドロキシベンゾフェノン系紫外線吸収剤類、フェ
ニルサリチレート等のサリチル酸エステル系紫外線吸収
剤類、あるいは粒径１μｍ以下の酸化亜鉛、酸化鉄等の
無機系の化合物が使用される。更に、耐候性（特に耐光
性）を向上させる為には、上記紫外線吸収剤等に加え
て、ラジカル捕捉剤としてヒンダードアミン系の光安定
剤を０．３〜２重量％、より好ましくは０．３〜０．５
重量％添加すると良い。２重量％を越えると、外装用、
浴室用として要求される煮沸水に浸漬し１０時間加熱に
より、剥離層表面が白化する為、好ましくない。また、
０．３重量％未満だと光安定剤の効果が発現されない。A light stabilizer is added to the peeling layer 3 if necessary in order to prevent deterioration due to ultraviolet rays. For example, 2- (2'-hydroxy-3 ', 5'-di-ter
t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 '-Tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'- Hydroxy-3'-isobutyl-
2'-Hydroxyphenyl-5-chlorobenzotriazole type UV absorbers such as 5'-propylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl 2'-hydroxyphenylbenzotriazole type ultraviolet absorbers such as phenyl) benzotriazole and 2- (2'-hydroxy-5'-methylphenyl) benzotriazole;
2'-dihydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone and other 2,2'-dihydroxybenzophenone ultraviolet absorbers, 2-hydroxy-4-methoxy 2-Hydroxybenzophenone type UV absorbers such as benzophenone and 2,4-dihydroxybenzophenone, salicylate type UV absorbers such as phenyl salicylate, or inorganic type such as zinc oxide and iron oxide having a particle size of 1 μm or less. A compound is used. Furthermore, in order to improve weather resistance (particularly light resistance), in addition to the above-mentioned ultraviolet absorber and the like, a hindered amine light stabilizer as a radical scavenger is used in an amount of 0.3 to 2% by weight, and more preferably 0.3. ~ 0.5
It is good to add weight%. If it exceeds 2% by weight,
It is not preferable because the surface of the release layer is whitened by immersing in boiling water required for bathroom and heating for 10 hours. Also,
If it is less than 0.3% by weight, the effect of the light stabilizer is not exhibited.
【００１３】装飾層４は、耐候性において優れた特性を
発揮するアクリル系樹脂をビヒクルの主体とする印刷層
からなる。装飾層４の形成に使用する印刷インキ中の着
色剤は、通常のグラビアインキに使用する着色剤であっ
てもよいが、例えば、ベンガラ、二酸化チタン、朱、群
青、緑青（塩基性炭酸銅）、カーボンブラック等の無機
質顔料や、フタロシアニン顔料、キナクリドン系顔料や
イソインドリノン系顔料等の縮合多環状顔料等の有機質
顔料などが、耐候性の面で優れた特性を発揮する。印刷
する絵柄としては、例えば木目模様、大理石模様等の天
然物模様、全面ベタ、幾何学模様、文字、記号等があ
る。The decorative layer 4 is composed of a printed layer mainly composed of an acrylic resin which exhibits excellent weather resistance. The colorant in the printing ink used for forming the decorative layer 4 may be a colorant used in a normal gravure ink, for example, red iron oxide, titanium dioxide, vermilion, ultramarine blue, patina (basic copper carbonate). Inorganic pigments such as carbon black and organic pigments such as phthalocyanine pigments, condensed polycyclic pigments such as quinacridone pigments and isoindolinone pigments exhibit excellent weather resistance. The pattern to be printed includes, for example, a natural pattern such as a wood grain pattern, a marble pattern, a solid pattern, a geometric pattern, letters, and symbols.
【００１４】接着剤層５は、塩化ビニル系樹脂基材への
接着力、耐熱性及び耐水性の面で塩化ビニル・酢酸ビニ
ル共重合体樹脂が使用される。特に、優れた耐熱水性、
耐湿熱性を発揮する点で、塩化ビニル・酢酸ビニル共重
合体樹脂の二次転移温度（Ｔｇ）が１００〜１１０℃
で、且つ平均分子量が６００００〜８００００の範囲に
ある樹脂であることが好ましい。Ｔｇが１００℃未満で
あったり、あるいは平均分子量が６００００未満である
場合には、転写層の屋外暴露、浴室内での熱水環境下で
の密着性が不十分となり、煮沸水１０時間浸漬での剥離
を防ぐことが出来ない。さらに、Ｔｇが低くなると塗膜
が乾燥固化後も粘着性が残り、転写箔を巻き取る時に、
ブロッキングが発生する。逆に、Ｔｇが１１０℃を越え
たり、あるいは平均分子量が８００００を越える場合に
は、塩化ビニル系樹脂基材を熱で変形、劣化させない温
度では被転写基材との初期密着力が十分に得られない。
このような特定の塩化ビニル・酢酸ビニル共重合体樹脂
を用いることにより、１００℃の熱水中で１０時間煮沸
しても、転写層の塩化ビニル系樹脂基材からの剥脱、ふ
くれ、変色等の異常発生がない化粧材となる。また、こ
のような樹脂を用いることにより、被転写基材の表面の
平滑性が悪い場合でも均一な転写が得られる転写箔とな
る。接着剤層５の厚みは、通常１〜５０μｍ（乾燥塗布
重量で１〜３６g/m2）程度である。For the adhesive layer 5, a vinyl chloride / vinyl acetate copolymer resin is used in terms of adhesive strength to a vinyl chloride resin base material, heat resistance and water resistance. In particular, excellent hot water resistance,
The vinyl chloride / vinyl acetate copolymer resin has a second-order transition temperature (Tg) of 100 to 110 ° C. from the viewpoint of exhibiting heat and humidity resistance.
And a resin having an average molecular weight of 60,000 to 80,000 is preferable. If the Tg is less than 100 ° C or the average molecular weight is less than 60,000, the transfer layer is exposed to the outdoors, and the adhesion in the hot water environment in the bathroom becomes insufficient, and the boiling water is immersed for 10 hours. Cannot be prevented from peeling. Furthermore, when Tg becomes low, the adhesiveness remains even after the coating is dried and solidified, and when the transfer foil is wound up,
Blocking occurs. On the other hand, when the Tg exceeds 110 ° C. or the average molecular weight exceeds 80,000, the vinyl chloride resin base material is sufficiently deformed and deteriorated by heat to obtain sufficient initial adhesion to the transfer base material. I can't.
By using such a specific vinyl chloride / vinyl acetate copolymer resin, even if it is boiled in hot water at 100 ° C. for 10 hours, the transfer layer is exfoliated from the vinyl chloride resin substrate, swelling, discoloration, etc. It is a cosmetic material that does not cause abnormalities. Further, by using such a resin, a transfer foil can be obtained in which uniform transfer can be obtained even when the surface of the transferred substrate has poor smoothness. The thickness of the adhesive layer 5 is usually about 1 to 50 μm (1 to 36 g / m 2 as a dry coating weight).
【００１５】本発明に係る塩化ビニル系樹脂基材用転写
箔の被転写基材を構成する塩化ビニル系樹脂としては、
塩化ビニルの単独重合体である塩化ビニル樹脂、塩化ビ
ニルと、エチレン、プロピレン、アクリル酸エステル、
メタクリル酸エステル等の他の重合性ビニル単量体との
共重合体樹脂、塩素化塩化ビニル樹脂等の塩化ビニル樹
脂又は前記共重合体樹脂を変性した変性樹脂、あるいは
塩化ビニル樹脂、前記共重合体樹脂、前記変性樹脂にア
クリル系樹脂、塩素化ポリエチレン、エチレン・酢酸ビ
ニル共重合体樹脂等の他の樹脂をブレンドしたブレンド
樹脂などが挙げられる。これらの樹脂の平均重合度とし
ては、大体７００〜２０００程度のものを選択する。こ
れらの塩化ビニル系樹脂には、必要に応じ、可塑剤、熱
安定剤、充填剤、難燃剤等を添加する。可塑剤として
は、フタル酸ジオクチル、フタル酸ジブチル等のフタル
酸エステル類、トリクレジルフォスファイト等の燐酸エ
ステル類、塩化パラフィン、トリメリット酸或いはエポ
キシ化大豆油等の化合物であり、外装、水回り用として
は、通常、最大３０重量部程度の添加量である。熱安定
剤としは、鉛、錫、カドミウム、バリウム、マグネシウ
ム、又はカルシウム等のカルボン酸塩、金属石鹸、キレ
ーター等である。また、被転写基材としては前記塩化ビ
ニル系樹脂から押出成形、射出成形、プレス成形等によ
り成形してなる、平板又は曲面板、棒状体等の各種形状
の成形体や基材、あるいは、成形体表面が塩化ビニル系
樹脂から構成されている成形体や基材に適用できる。The vinyl chloride resin constituting the transferred substrate of the transfer foil for vinyl chloride resin substrate according to the present invention includes:
Vinyl chloride resin which is a homopolymer of vinyl chloride, vinyl chloride and ethylene, propylene, acrylic ester,
Copolymer resin with other polymerizable vinyl monomer such as methacrylic acid ester, vinyl chloride resin such as chlorinated vinyl chloride resin, or modified resin obtained by modifying the copolymer resin, or vinyl chloride resin, the above-mentioned copolymer Examples thereof include a united resin and a blend resin obtained by blending the above modified resin with another resin such as an acrylic resin, chlorinated polyethylene, and an ethylene / vinyl acetate copolymer resin. The average degree of polymerization of these resins is selected to be approximately 700 to 2000. If necessary, a plasticizer, a heat stabilizer, a filler, a flame retardant, etc. are added to these vinyl chloride resins. Examples of the plasticizer include dioctyl phthalate, dibutyl phthalate and other phthalates, tricresyl phosphite and other phosphate esters, chlorinated paraffins, trimellitic acid, epoxidized soybean oil, and other compounds. For general use, the maximum addition amount is about 30 parts by weight. Examples of the heat stabilizer include carboxylates such as lead, tin, cadmium, barium, magnesium or calcium, metal soaps, chelators and the like. Further, as the transferred substrate, a molded body or substrate of various shapes such as a flat plate or a curved plate or a rod-shaped body formed by extrusion molding, injection molding, press molding or the like from the vinyl chloride resin, or molded It can be applied to a molded body or a base material whose body surface is made of vinyl chloride resin.
【００１６】[0016]
【作用】本発明に係る塩化ビニル系樹脂基材用転写箔に
よれば、被転写基材に転写後の転写層の最上層となる剥
離層がアクリル系樹脂又は塩化ビニル・酢酸ビニル共重
合体樹脂とアクリル系樹脂との混合物とからなる組成物
であって、特に当該組成物にワックス又は／及び減摩剤
とが含有されている結果、耐候性及び耐摩性に対して特
に優れた転写層の物性を発揮する。また、接着剤層にポ
リ塩化ビニル・酢酸ビニル共重合体樹脂において、二次
転移温度（Ｔｇ）が１００〜１１０℃で、且つ平均分子
量が６００００〜８００００の特定の樹脂を使用する結
果、転写層が塩化ビニル系樹脂基材に良好に密着し、最
大煮沸水浸漬１０時間でも、剥離、ふくれ、黄変のな
い、耐熱水性、耐湿熱性に優れた転写層の物性を発揮す
る。According to the transfer foil for a vinyl chloride resin base material of the present invention, the release layer, which is the uppermost layer of the transfer layer after being transferred to the transfer base material, is an acrylic resin or a vinyl chloride / vinyl acetate copolymer. A composition comprising a resin and a mixture of an acrylic resin, which is particularly excellent in weather resistance and abrasion resistance as a result of containing wax or / and an anti-friction agent in the composition. Exert the physical properties of. Further, as a result of using a specific resin having a second-order transition temperature (Tg) of 100 to 110 ° C. and an average molecular weight of 60,000 to 80,000 in the polyvinyl chloride / vinyl acetate copolymer resin for the adhesive layer, the transfer layer Adheres well to the vinyl chloride resin base material, and exhibits the physical properties of the transfer layer excellent in hot water resistance and wet heat resistance without peeling, swelling, or yellowing even after the maximum immersion in boiling water for 10 hours.
【００１７】《実施例》以下、本発明に係る塩化ビニル
系樹脂基材用転写箔について具体的な構成を実施例に基
づいて説明する。転写箔基材として、ポリエチレンテレ
フタレートフィルム（東レ（株）製 ｘ−４５ 厚さ２
５μｍ）を用い、その片面に、剥離層用として塩化ビニ
ル・酢酸ビニル共重合体樹脂とアクリル系樹脂との混合
樹脂（重量比で塩化ビニル・酢酸ビニル共重合体樹脂：
アクリル系樹脂＝２：８）１００重量％に対して、ポリ
エチレンワックスを３重量％、シリカを１重量％、紫外
線吸収剤としてベンゾフェノン系のものを０．３重量％
添加したインキを、機械彫刻グラビアベタ版（ヘル社の
ヘリオクリショグラフで彫刻、線数４８／cm、角度設定
０度）を用い、３回の重ね刷りを行い、乾燥重量で５g/
m2の剥離層を形成した。<Example> A specific structure of the transfer foil for vinyl chloride resin base material according to the present invention will be described below with reference to Examples. As a transfer foil substrate, a polyethylene terephthalate film (manufactured by Toray Industries, Inc., x-45, thickness 2
5 μm), and on one side thereof, a mixed resin of vinyl chloride / vinyl acetate copolymer resin and acrylic resin for the release layer (vinyl chloride / vinyl acetate copolymer resin by weight ratio:
Acrylic resin = 2: 8) 100% by weight, 3% by weight of polyethylene wax, 1% by weight of silica, 0.3% by weight of benzophenone type as an ultraviolet absorber
The added ink was mechanically engraved with a gravure solid plate (engraved with Helio's Heliocrisograph, line number 48 / cm, angle setting 0 degree), and overprinted 3 times. Dry weight 5g /
An m 2 release layer was formed.
【００１８】次いで、装飾層を、アクリル系樹脂と塩化
ビニル・酢酸ビニル共重合体樹脂とを１：１重量比で混
合した混合樹脂をビヒクルし、キナクリドンとイソイン
ドリノンとカーボンブラックとを顔料とするグラビアイ
ンキによる木目絵柄印刷層と、同じ混合樹脂をビヒクル
とし、二酸化チタンとキナクリドンとイソインドリノン
とを顔料とするグラビアインキによる着色ベタ刷り層と
により、形成した。Next, the decorative layer was vehicled with a mixed resin in which an acrylic resin and a vinyl chloride / vinyl acetate copolymer resin were mixed at a 1: 1 weight ratio, and quinacridone, isoindolinone, and carbon black were used as pigments. And a colored solid printing layer with a gravure ink containing titanium dioxide, quinacridone, and isoindolinone as pigments using the same mixed resin as a vehicle.
【００１９】しかる後、塩化ビニル・酢酸ビニル共重合
体樹脂（Ｔｇ＝１０５℃、平均分子量８０，０００によ
る接着剤層の形成を、溶剤希釈したインキを、リバース
ロールコート法を用いて塗工し、乾燥重量で１０g/m2の
接着剤層を設けた。以上にて、本発明に係る塩化ビニル
系樹脂基材用転写箔を作成した。Thereafter, a vinyl chloride / vinyl acetate copolymer resin (Tg = 105 ° C., formation of an adhesive layer having an average molecular weight of 80,000) was coated with a solvent-diluted ink using a reverse roll coating method. An adhesive layer having a dry weight of 10 g / m 2 was provided, and the transfer foil for vinyl chloride resin base material according to the present invention was prepared.
【００２０】次いで、被転写基材として硬質塩化ビニル
樹脂の押し出し成形体からなる外装材基材の表面に、前
記の塩化ビニル系樹脂基材用転写箔を当接して、表面温
度１８０℃のシリコンゴムロールを用い熱圧を加え、塩
化ビニル系樹脂基材用転写箔の転写層を被転写基材表面
に転写して、外装化粧材を得た。得られた外装化粧材の
耐摩性を、テーバー摩耗試験ＣＳ−１７、摩耗輪５００
ｇ荷重、２００回転まで試験したところ、装飾層の絵柄
が取れること無く、充分な性能を発揮した。また、ニチ
バン（株）の工業用セロテープ・２５mm幅を転写層の表
面に貼着後剥離するセロハンテープ剥離試験でも絵柄剥
離はなかった。さらに、１００℃の熱水中で１０時間煮
沸後も、転写層には剥脱、ふくれ、変色等の異常が認め
られず、セロハンテープ剥離試験でも絵柄が剥離せず良
好で充分な耐熱水性を発揮した。くわえて、得られた外
装化粧材をカーボンアーク燈サンシャインウエザオメー
タ（ブラックパネル温度６３℃）にて、１０００時間暴
露したところ、目視で判別できる程の変退色、転写層の
剥脱ともになかった。Then, the transfer foil for a vinyl chloride resin base material is brought into contact with the surface of an exterior material base material made of an extruded product of a hard vinyl chloride resin as a transfer base material, and a silicone having a surface temperature of 180 ° C. A rubber roll was used to apply heat and pressure to transfer the transfer layer of the transfer foil for the vinyl chloride resin base material onto the surface of the transfer target material to obtain an exterior decorative material. The abrasion resistance of the obtained exterior decorative material was measured by Taber abrasion test CS-17, abrasion ring 500.
When tested under g load and up to 200 rotations, sufficient performance was exhibited without removing the pattern of the decorative layer. In addition, no pattern was peeled off in a cellophane tape peeling test in which a 25 mm wide industrial cellophane tape of Nichiban Co., Ltd. was adhered to the surface of the transfer layer and then peeled off. Furthermore, even after boiling for 10 hours in hot water at 100 ° C, no abnormalities such as exfoliation, blistering, discoloration, etc. were observed in the transfer layer, and the pattern did not peel off in the cellophane tape peeling test, showing sufficient hot water resistance. did. In addition, when the obtained exterior decorative material was exposed to a carbon arc lamp sunshine weatherometer (black panel temperature 63 ° C.) for 1000 hours, discoloration and fading of the transfer layer which could be visually discerned were not observed.
【００２１】《比較例１》接着剤層用のインキにて、塩
化ビニル・酢酸ビニル共重合体樹脂のＴｇ＝６０℃、平
均分子量２４，８００とした他は、実施例と同じにして
行った。その結果、転写性は良好であり、テーバー摩耗
試験（実施例と同一条件）、及び沸騰水浸漬前のセロハ
ンテープ剥離試験でも、絵柄の剥離はないが、１００℃
の煮沸水に浸漬し１０時間加熱した結果、転写層は一部
分、剥脱、ふくれを生じでいた。Comparative Example 1 An ink for an adhesive layer was prepared in the same manner as in Example 1 except that the vinyl chloride / vinyl acetate copolymer resin had a Tg of 60 ° C. and an average molecular weight of 24,800. . As a result, the transferability was good, and even in the Taber abrasion test (the same conditions as in the example) and the cellophane tape peeling test before immersion in boiling water, the pattern did not peel, but at 100 ° C.
As a result of immersion in boiling water for 10 hours and heating for 10 hours, the transfer layer partially exfoliated and blisters.
【００２２】《比較例２》接着剤層用のインキにて、塩
化ビニル・酢酸ビニル共重合体樹脂のＴｇ＝１１５℃、
平均分子量９５，０００とした他は、実施例と同じにし
て行った。その結果、転写後、沸騰水浸漬前のセロハン
テープ剥離試験で、既に絵柄が剥離してしまった。Comparative Example 2 With the ink for the adhesive layer, Tg of the vinyl chloride / vinyl acetate copolymer resin was 115 ° C.,
The procedure was the same as in the example except that the average molecular weight was 95,000. As a result, after transfer, the pattern had already peeled off in the cellophane tape peeling test before immersion in boiling water.
【００２３】[0023]
【発明の効果】本発明は、以上説明したように構成され
ているので、以下に記載されるような効果を奏する。本
発明の塩化ビニル系樹脂基材用転写箔は、通常の転写箔
の転写工程によって、塩化ビニル系樹脂の基材の表面に
対して化粧が可能であり、得られた化粧材は、表面の平
滑性の悪い塩化ビニル樹脂の押し出し成形体であって
も、鮮明な絵柄を的確に表現可能であり、更に剥離層に
ワックス、減摩剤を添加して耐摩性を向上させている為
に、外装材、特に、簀の子、樹脂タイル等に用いた場合
でも、充分な性能の耐摩性が得られ、且つ樹脂タイルで
は歩行時の滑り易さも抑えられるという顕著な効果を奏
する。Since the present invention is constructed as described above, it has the following effects. The transfer foil for vinyl chloride resin base material of the present invention can be applied to the surface of the base material of vinyl chloride resin by the transfer process of a normal transfer foil, and the obtained decorative material is Even if it is an extrusion molded product of vinyl chloride resin with poor smoothness, it is possible to accurately express a clear pattern, and since wax and a lubricant are added to the release layer to improve the wear resistance, Even when it is used for an exterior material, particularly a bowl, a resin tile, etc., it has a remarkable effect that sufficient abrasion resistance can be obtained and the resin tile also suppresses slipperiness during walking.
【００２４】くわえて、接着剤層を形成する塩化ビニル
・酢酸ビニル共重合体樹脂の二次転移点（Ｔｇ）及び平
均分子量を特定したものを用いることにより、塩化ビニ
ル系樹脂基材に転写層を転写・接着した化粧材の、耐熱
水性、耐湿熱性が良好であり、外装用の塩化ビニル系樹
脂部材に要求される「１００℃熱水中での１０時間煮沸
後も、転写層の剥脱、ふくれ、変色等の異常を生じない
だけの耐熱水、耐温水性」を充分に満たすという顕著な
効果を奏するものである。In addition, a transfer layer is formed on a vinyl chloride resin base material by using a vinyl chloride / vinyl acetate copolymer resin forming the adhesive layer, which has a specified second-order transition point (Tg) and average molecular weight. The heat-resistant water resistance and moisture-heat resistance of the decorative material that has been transferred and adhered are good, and the transfer layer peels off after boiling for 10 hours in hot water at 100 ° C, which is required for vinyl chloride resin members for exterior packaging. It has a remarkable effect of sufficiently satisfying "heat-resistant water and hot-water resistance that does not cause abnormalities such as blistering and discoloration".
【図１】本発明の塩化ビニル系樹脂基材用転写箔の一実
施例を示す縦断面図。FIG. 1 is a longitudinal sectional view showing an embodiment of a transfer foil for vinyl chloride resin base material of the present invention.
１ 塩化ビニル系樹脂基材用転写箔 ２ 転写箔基材 ３ 剥離層 ４ 装飾層 ４ａ 絵柄 ５ 接着剤層 ６ 転写層 ７ 減摩剤、ワックス 1 Transfer foil for vinyl chloride resin base material 2 Transfer foil base material 3 Release layer 4 Decorative layer 4a Picture 5 Adhesive layer 6 Transfer layer 7 Lubricant, wax
Claims (2)
樹脂又は塩化ビニル・酢酸ビニル共重合体樹脂とアクリ
ル系樹脂との混合樹脂にワックス又は／及び減摩剤を添
加した剥離層と、アクリル系樹脂をビヒクルの主成分と
する印刷層による装飾層と、塩化ビニル・酢酸ビニル共
重合体樹脂からなる接着剤層とが順次積層されているこ
とを特徴とする塩化ビニル系樹脂基材用転写箔。1. A release layer formed by adding a wax and / or an anti-friction agent to an acrylic resin or a mixed resin of an acrylic resin or a vinyl chloride / vinyl acetate copolymer resin and an acrylic resin on one surface of a transfer foil substrate. A vinyl chloride resin base, wherein a decorative layer made of a printed layer containing an acrylic resin as a main component of the vehicle and an adhesive layer made of a vinyl chloride / vinyl acetate copolymer resin are sequentially laminated. Transfer foil for materials.
酸ビニル共重合体樹脂の二次転移温度（Ｔｇ）が１００
〜１１０℃で、且つ平均分子量が６００００〜８０００
０であることを特徴とする請求項１記載の塩化ビニル系
樹脂基材用転写箔。2. The second-order transition temperature (Tg) of the vinyl chloride / vinyl acetate copolymer resin constituting the adhesive layer is 100.
~ 110 ° C and average molecular weight 60,000-8,000
It is 0, The transfer foil for vinyl chloride resin base materials of Claim 1 characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5198822A JPH0732718A (en) | 1993-07-19 | 1993-07-19 | Transfer foil for vinyl chloride resin base material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5198822A JPH0732718A (en) | 1993-07-19 | 1993-07-19 | Transfer foil for vinyl chloride resin base material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0732718A true JPH0732718A (en) | 1995-02-03 |
Family
ID=16397496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5198822A Pending JPH0732718A (en) | 1993-07-19 | 1993-07-19 | Transfer foil for vinyl chloride resin base material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0732718A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997047392A1 (en) | 1996-06-10 | 1997-12-18 | Nippon Telegraph And Telephone Corporation | Two-fluid nozzle and device employing the same nozzle for freezing and drying liquid containing biological substances |
| KR100381255B1 (en) * | 1996-11-26 | 2003-06-18 | 주식회사 코오롱 | Stamping foil |
| KR100749282B1 (en) * | 2001-07-30 | 2007-08-14 | 주식회사 코오롱 | Reflective film for CRT panel |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6238170U (en) * | 1985-08-24 | 1987-03-06 | ||
| JPH03239599A (en) * | 1990-02-15 | 1991-10-25 | Dainippon Printing Co Ltd | Transfer foil for vinyl chloride resin molded body |
| JPH044200A (en) * | 1990-04-20 | 1992-01-08 | Oike Ind Co Ltd | Hard coat transfer foil |
| JPH0473183A (en) * | 1990-05-30 | 1992-03-09 | Dainippon Printing Co Ltd | Transfer sheet for exterior decorative material |
-
1993
- 1993-07-19 JP JP5198822A patent/JPH0732718A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6238170U (en) * | 1985-08-24 | 1987-03-06 | ||
| JPH03239599A (en) * | 1990-02-15 | 1991-10-25 | Dainippon Printing Co Ltd | Transfer foil for vinyl chloride resin molded body |
| JPH044200A (en) * | 1990-04-20 | 1992-01-08 | Oike Ind Co Ltd | Hard coat transfer foil |
| JPH0473183A (en) * | 1990-05-30 | 1992-03-09 | Dainippon Printing Co Ltd | Transfer sheet for exterior decorative material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997047392A1 (en) | 1996-06-10 | 1997-12-18 | Nippon Telegraph And Telephone Corporation | Two-fluid nozzle and device employing the same nozzle for freezing and drying liquid containing biological substances |
| KR100381255B1 (en) * | 1996-11-26 | 2003-06-18 | 주식회사 코오롱 | Stamping foil |
| KR100749282B1 (en) * | 2001-07-30 | 2007-08-14 | 주식회사 코오롱 | Reflective film for CRT panel |
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