JP3006866B2 - Transfer foil - Google Patents
Transfer foilInfo
- Publication number
- JP3006866B2 JP3006866B2 JP2280237A JP28023790A JP3006866B2 JP 3006866 B2 JP3006866 B2 JP 3006866B2 JP 2280237 A JP2280237 A JP 2280237A JP 28023790 A JP28023790 A JP 28023790A JP 3006866 B2 JP3006866 B2 JP 3006866B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- release layer
- transfer
- release
- transfer foil
- 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 - Lifetime
Links
Landscapes
- Decoration By Transfer Pictures (AREA)
- Laminated Bodies (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は転写後の耐摩耗性及び透明性に優れた透明な
剥離層を有する転写箔に関する。The present invention relates to a transfer foil having a transparent release layer excellent in abrasion resistance and transparency after transfer.
従来から被転写体に絵柄等の意匠を付与する手段の一
つとして転写箔が用いられている。この転写箔は離型性
の基材シート表面に、剥離層、絵柄層、金属蒸着層等の
装飾層、接着剤層等で形成した転写層を積層した構成を
有している。2. Description of the Related Art Conventionally, a transfer foil has been used as one of means for imparting a design such as a picture to a transferred body. This transfer foil has a configuration in which a release layer, a pattern layer, a decorative layer such as a metal vapor deposition layer, and a transfer layer formed of an adhesive layer and the like are laminated on the surface of a releasable base material sheet.
そして上記の転写層の接着剤層と成型品等の被写体表
面が接するように転写箔を載置し、その上から加熱もし
くは加圧等の手段を用いて転写層を被転写体に接着させ
た後、基材シートを剥離することにより成型品等の表面
に絵柄や金属蒸着模様を付与することができる。Then, the transfer foil was placed so that the adhesive layer of the transfer layer and the surface of the object such as a molded product were in contact with each other, and the transfer layer was adhered to the transfer object using a means such as heating or pressing from above. Thereafter, a pattern or a metal vapor-deposited pattern can be provided on the surface of a molded product or the like by peeling the substrate sheet.
上記の転写方法の一つとして成型品の成型と同時に転
写を行う成型同時転写方法が知られている。これは、上
記の転写箔を射出成型金型内に載置し、成型材料として
の溶融樹脂を金型内に射出充填した後に成型品を脱型し
基材フィルムを剥離して射出成型品の表面に意匠を付与
する方法であり、この方法は成型品の形状が曲面であっ
ても転写が容易であり、広く用いられている。As one of the above-described transfer methods, a simultaneous molding transfer method in which transfer is performed simultaneously with molding of a molded product is known. This is done by placing the above-mentioned transfer foil in an injection molding die, injecting a molten resin as a molding material into the die, removing the molded product, peeling the base film, and removing the injection molded product. This is a method of imparting a design to the surface. This method is easy to transfer even if the shape of a molded product is a curved surface, and is widely used.
このような種々の転写に用いられる転写箔の剥離層
は、通常熱可塑性樹脂を用いて形成されることが多かっ
た。これは例えば反応硬化型の樹脂を用いると、転写箔
製造時に樹脂の硬化に時間がかかり作業性が低下してし
まう。また製造した転写箔を60℃で1週間程度巻き取っ
たまま保存してエージングを行った場合、ブロッキング
をおこしてしまう等の問題があった。更に上記の成型同
時転写のように曲面等に転写を行う際、転写層の樹脂は
柔軟性を要求される等の理由から熱可塑性樹脂がよく用
いられていた。The release layer of the transfer foil used for such various kinds of transfer is usually formed using a thermoplastic resin in many cases. For example, when a reaction-curable resin is used, it takes a long time to cure the resin during the production of the transfer foil, and the workability is reduced. In addition, when the produced transfer foil is stored and wound up at 60 ° C. for about one week and then aged, there is a problem that blocking occurs. Further, when performing transfer onto a curved surface or the like as in the above-described simultaneous transfer of molding, a thermoplastic resin is often used for the resin of the transfer layer because flexibility is required.
一方、剥離層は転写箔使用時の基材シートとの剥離を
容易ならしめることに加えて、被転写体に転写を行った
後に、被転写体の最表面を形成して下層となる金属蒸着
や絵柄等の意匠を保護層としての機能を有する。そのた
めに剥離層は耐摩耗性が要求されることが多く、この耐
摩耗性を向上させる手段として通常剥離層の中にワッ
クスを添加する、剥離層の層厚みを厚くする等の対応
がなされていた。On the other hand, the release layer facilitates the separation from the substrate sheet when using the transfer foil, and after the transfer to the transfer target, forms the outermost surface of the transfer target and forms the lower layer by metal deposition. It has a function as a protective layer for designs such as images and designs. For this reason, the release layer is often required to have abrasion resistance, and as a means for improving the abrasion resistance, measures such as adding wax to the release layer or increasing the thickness of the release layer have been taken. Was.
しかしながら、上記の剥離層へのワックスの添加
は、該層内の光を散乱させて剥離層の透明性を低下させ
てしまうという問題があった。またの場合も同様に剥
離層の厚みを厚くすると透明性が低下することや樹脂の
使用量が増えて転写箔の原料コストが上昇してしまう等
の問題があり、いずれにしても耐摩耗性を改良しようと
すると剥離層の透明性が低下することは避けられない問
題であった。However, there is a problem that the addition of the wax to the release layer scatters light in the layer and lowers the transparency of the release layer. Also in this case, if the thickness of the release layer is similarly increased, there is a problem that the transparency is reduced, the amount of resin used is increased, and the raw material cost of the transfer foil is increased. It is an unavoidable problem that the transparency of the release layer is reduced when trying to improve.
また上記の問題は、特に剥離層の樹脂に熱可塑性樹脂
を用いた場合に大きな問題があり、例えば、転写時に熱
の加わる成型同時転写等の場合に、熱可塑性樹脂の融点
に近い温度で樹脂に分散しているワックスが装飾層の表
面に移行したりブリードを起こして、転写後に剥離層の
下層となる絵柄や金属蒸着等の意匠に対して白化や曇り
等の悪影響を及ぼし意匠性を著しく低下させてしまう虞
れがあった。In addition, the above problem has a significant problem particularly when a thermoplastic resin is used as the resin of the release layer.For example, in the case of simultaneous molding transfer where heat is applied at the time of transfer, the resin is heated at a temperature close to the melting point of the thermoplastic resin. The wax dispersed on the surface of the decorative layer migrates or causes bleeding, which has a negative effect such as whitening or clouding on designs such as a pattern or metal vapor deposition which is the lower layer of the release layer after transfer, and significantly reduces the design. There was a risk of lowering.
本発明は上記従来技術の欠点を解消し、剥離層の透明
性と耐摩耗性に優れた転写箔を提供することを目的とす
るものである。An object of the present invention is to solve the above-mentioned drawbacks of the prior art and to provide a transfer foil excellent in transparency and abrasion resistance of a release layer.
本発明は、(1)剥離性基材の表面に透明部を有する
剥離層、装飾層を順次積層してなる転写箔において、上
記剥離層を2層以上から形成し、最も剥離性基材側に設
けた剥離層に、数平均分子量が1000〜8000で形状が花弁
状あるいは鱗片状のポリエチレンワックスを含有せし
め、且つ最も装飾層側の剥離層に、数平均分子量が500
〜3000で形状が塊状のポリエチレンワックスを含有せし
め該剥離層のヘイズ値が単層で5%以下になるように形
成したことを特徴とする転写箔、(2)剥離層のワック
スの含有量を最も剥離性基材側の剥離層から装飾層側の
剥離層に行くに従って順次減少するように設けた上記
(1)記載の転写箔、を要旨とするものである。The present invention provides (1) a transfer foil in which a release layer having a transparent portion on the surface of a peelable substrate and a decorative layer are sequentially laminated, wherein the release layer is formed of two or more layers, The release layer provided has a number-average molecular weight of 1000 to 8000 and contains a petal-like or scaly polyethylene wax, and the release layer closest to the decoration layer has a number-average molecular weight of 500.
(2) a transfer foil characterized in that the release layer is formed so that the haze value of the release layer is 5% or less in a single layer by incorporating polyethylene wax having a bulk shape of up to 3000. The transfer foil according to the above (1), which is provided so as to decrease in order from the release layer on the most releasable substrate side to the release layer on the decorative layer side.
以下、本発明の実施例を図面に基づき説明する。図面
は本発明の一実施例を示し、第1図は本発明転写箔の一
例を示す縦断面図である。Hereinafter, embodiments of the present invention will be described with reference to the drawings. The drawings show an embodiment of the present invention, and FIG. 1 is a longitudinal sectional view showing an example of the transfer foil of the present invention.
本発明転写箔1は剥離性基材2の表面に全面が透明な
剥離層3、装飾層としての絵柄層4、接着剤層5を順次
積層してなる転写層6を形成した転写箔であり、上記剥
離層3が剥離層3Aと剥離層3Bとからなる2層から形成さ
れ、最も剥離性基材2側に設けられた剥離層3Bはワック
スを含有し、最も装飾層4側に設けた剥離層3Aは単層で
のヘイズ値が5%以下である構成を有する。The transfer foil 1 of the present invention is a transfer foil having a transfer layer 6 formed by sequentially laminating a release layer 3 having a transparent surface, a picture layer 4 as a decorative layer, and an adhesive layer 5 on the entire surface of a peelable substrate 2. The release layer 3 is formed of two layers consisting of a release layer 3A and a release layer 3B, and the release layer 3B provided on the most exfoliable substrate 2 side contains wax and is provided on the decorative layer 4 side. The release layer 3A has a single layer haze value of 5% or less.
本発明は剥離層を2層以上設けて最も剥離性基材側の
剥離層に耐摩耗性の機能を付与し、最も装飾層側の剥離
層には透明性を阻害せず装飾層に悪影響を与えないよう
に構成したことに特徴を有する。In the present invention, two or more release layers are provided to impart a wear-resistant function to the release layer closest to the releasable substrate, and the release layer closest to the decoration layer does not impair transparency and does not adversely affect the decoration layer. The feature is that it is configured not to give.
尚本発明では剥離層3の透明部は、全面でもまた部分
的でもどちらでもよい。また透明とは無色透明、着色透
明のいずれでもよい。また剥離層は2層以上であれば何
層でもよいが、箔ギレ性、表面強度、外観など考慮する
と通常2層程度が好ましい。In the present invention, the transparent portion of the release layer 3 may be either the entire surface or a partial region. Transparent may be either colorless and transparent. The release layer may be any number of layers as long as it is two or more layers, but is usually preferably about two layers in consideration of foil crepe, surface strength, appearance, and the like.
剥離層3Aは、単層でのヘイズ値が5%以下であれば材
質は特に限定されないが、樹脂材質に剥離層3B及び装飾
層4と接着性のよいものを選定するのが好ましい。また
剥離層3Bは、剥離性基材2と剥離性を有し、且つ転写終
了後は転写層6の表面保護層として所望の物性を有する
樹脂組成を選定する。The material of the release layer 3A is not particularly limited as long as the haze value of a single layer is 5% or less, but it is preferable to select a resin material having good adhesiveness to the release layer 3B and the decorative layer 4. In addition, the release layer 3B is selected from a resin composition having releasability from the releasable substrate 2 and having desired physical properties as a surface protective layer of the transfer layer 6 after the transfer.
剥離層3Aのヘイズ値とは、曇り値のことで(1)式に
示すように剥離層の散乱光線透過率と全光線透過率から
求めることができ、JISK6714に規定されたくもり価の試
験方法を用いる。The haze value of the release layer 3A is a haze value, which can be obtained from the scattered light transmittance and the total light transmittance of the release layer as shown in the equation (1). The haze value is defined by JIS K6714. Is used.
剥離層3に添加するワックスは特に限定されず、ワッ
クスの材質として例えば、ポリエチレンワックス、パラ
フィンワックス、フッ素樹脂系ワックス等の公知のワッ
クスを用いることかできる。またワックスの形状は、耐
摩耗性を要求される最も剥離性基材側の剥離層に添加す
る場合は、鱗片状や花弁状が好ましい。また透明性が要
求される最も装飾層側の剥離層に添加する場合には、塊
状が好ましい。 The wax added to the release layer 3 is not particularly limited, and known waxes such as polyethylene wax, paraffin wax, and fluororesin wax can be used as the wax material. When the wax is added to the release layer on the side of the most releasable substrate that requires abrasion resistance, the shape of the wax is preferably scaly or petal. In addition, when added to the release layer closest to the decorative layer where transparency is required, a lump is preferable.
ワックスの分子量はワックスの種類により異なるが、
上記のように透明性や摩耗性に大きく影響を与える。一
般にワックスの分子量が大きくなると耐摩耗性は向上す
るが透明性は低下し、分子量が小さくなると透明性が向
上し耐摩耗性が低下する。従って本発明では剥離性基材
側のワックスを分子量を大きいものを用いて、装飾層側
に近い剥離層に用いるものに分子量の小さいものを用い
ることが好ましい。The molecular weight of the wax depends on the type of wax,
As described above, it greatly affects transparency and abrasion. In general, when the molecular weight of the wax increases, the abrasion resistance improves, but the transparency decreases. When the molecular weight decreases, the transparency improves and the abrasion resistance decreases. Therefore, in the present invention, it is preferable to use a wax having a large molecular weight as the wax on the releasable base material side and to use a wax having a small molecular weight as the wax used for the release layer near the decorative layer side.
また、ワックスの添加量は、剥離層に使用する樹脂材
質、ワックスの種類等によっても異なるが、必要な摩耗
性が得られかつ装飾層との密着性等が剥離層に使用する
樹脂と物性を低下させない範囲で選定することができ
る。またワックスは各剥離層間の密着性をより向上させ
るために含有量を最も剥離性基材側の剥離層から装飾層
側の剥離層に行くに従って減少するように構成すること
がより好ましい。Further, the amount of the wax to be added depends on the resin material used for the release layer, the type of the wax, and the like. It can be selected within a range that does not lower it. Further, in order to further improve the adhesion between the release layers, it is more preferable that the content of the wax is reduced so as to go from the release layer on the release substrate side to the release layer on the decoration layer side.
最も剥離性基材側に設けた剥離層に含有せしめたワッ
クスには数平均分子量1000〜8000で形状が花弁状あるい
は鱗片状のポリエチレンワックスを用いることが特に好
ましく、また最も装飾層側に設けた剥離層に含有せしめ
たワックスには、数平均分子量が500〜3000で形状が塊
状のポリエチレンワックスを用いることが特に好まし
い。It is particularly preferable to use a petal-like or scale-like polyethylene wax with a number average molecular weight of 1,000 to 8,000 for the wax contained in the release layer provided on the most releasable substrate side, and also provided on the most decorative layer side. It is particularly preferable to use a polyethylene wax having a number average molecular weight of 500 to 3000 and a lump in shape as the wax contained in the release layer.
剥離層3に用いる樹脂材質は、表面の耐擦傷性、耐薬
品性、耐汚染性を要する場合、剥離層3Bに熱硬化性樹脂
又は電離放射線硬化性樹脂を用いることもできるが、本
発明の効果を最大限に発揮するためには、剥離層3A、3B
ともに熱可塑性樹脂を使用することが好ましい。The resin material used for the release layer 3 may be a thermosetting resin or an ionizing radiation-curable resin for the release layer 3B if the surface requires scratch resistance, chemical resistance, and stain resistance. To maximize the effect, release layers 3A and 3B
In both cases, it is preferable to use a thermoplastic resin.
熱可塑性樹脂として例えば、エチルセルロース、硝酸
セルロース、酢酸セルロース、エチルヒドロキシエチル
セルロース、セルロースアセテートプロピオネート等の
セルロース誘導体、ポリスチレン、ポリ−α−メチルス
チレン等のスチレン樹脂、またはスチレン共重合体、ポ
リメタクリル酸メチル、ポリメタクタル酸エチル、ポリ
アクリル酸エチル、ポリアクリル酸ブチル等のアクリル
樹脂、ポリ塩化ビニル、ポリ酢酸ビニル、塩化ビニル、
/酢酸ビニル共重合体、ポリビニルブチラール、ロジ
ン、ロジン変性マレイン酸樹脂、ロジン変性フェノール
樹脂、重合ロジン等のロジンエステル樹脂、クマロン樹
脂、ビニルトルエン樹脂、ポリアミド樹脂等の天然又は
合成樹脂が挙げられる。As the thermoplastic resin, for example, ethyl cellulose, cellulose nitrate, cellulose acetate, ethyl hydroxyethyl cellulose, cellulose derivatives such as cellulose acetate propionate, polystyrene, styrene resin such as poly-α-methylstyrene, or styrene copolymer, polymethacrylic acid Acrylic resin such as methyl, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, polyvinyl chloride, polyvinyl acetate, vinyl chloride,
/ Natural or synthetic resins such as vinyl acetate copolymer, polyvinyl butyral, rosin, rosin-modified maleic resin, rosin-modified phenol resin, rosin ester resin such as polymerized rosin, coumarone resin, vinyl toluene resin, polyamide resin and the like.
接着剤層5は、転写層6を被転写体に転移、接着させ
るための層で、感熱接着剤、溶剤活性型接着剤、電離放
射線硬化性接着剤等の中から用途に応じて選定する。
尚、絵柄層4、剥離層3A等の接着剤層5以外の転写層
が、それ自身に接着性を有する場合は、接着剤層5を省
略することもできる。The adhesive layer 5 is a layer for transferring and adhering the transfer layer 6 to an object to be transferred, and is selected from a heat-sensitive adhesive, a solvent-activated adhesive, an ionizing radiation-curable adhesive and the like according to the application.
When the transfer layer other than the adhesive layer 5 such as the pattern layer 4 and the release layer 3A has adhesiveness to itself, the adhesive layer 5 may be omitted.
上記の感熱接着剤は、加熱によって接着性が発現する
ものであり、通常熱可塑性樹脂、アイオノマー等が用い
られ、このような樹脂としてたとえば、上記の剥離層に
用いる熱可塑性樹脂と同様の樹脂や、それに加えてポリ
インソプレンゴム、ポリイソブチルゴム、スチレンブタ
ジエンゴム、ブタジエンアクリロニトリルゴム等のゴム
系樹脂、ポリ塩素化等の天然又は合成樹脂、各種アイオ
ノマー、或いは上記の2種以上の混合物等が挙げられ
る。The above-mentioned heat-sensitive adhesive is one in which adhesiveness is developed by heating, and usually a thermoplastic resin, an ionomer, or the like is used.For example, as such a resin, a resin similar to the thermoplastic resin used for the release layer or And rubber resins such as polyinsoprene rubber, polyisobutyl rubber, styrene butadiene rubber, butadiene acrylonitrile rubber, natural or synthetic resins such as polychlorinated resins, various ionomers, and mixtures of two or more of the above. Can be
剥離性基材2は転写層6(剥離層3B)と剥離性の良い
5〜200μm程度の基材フィルムを用いる。このような
基材フィルムの材質は例えばポリエチレンテレフタレー
ト、ポリブチレンテレフタレート、ポリエチレンテレフ
タレート/イソフタレートの共重合体等のポリエステル
樹脂、ポリエチレン、ポリプロピレン、ポリメチルペン
テン等のポリオレフィン樹脂、ポリフッ化ビニル、ポリ
フッ化ビニリデン、ポリ4フッ化エチレン、エチレン4
フッ化エチレン共重合体等のポリフッ化エチレン系樹
脂、ナイロン6、ナイロン66等のポリアミドポリ塩化ビ
ニル、塩化ビニル/酢酸ビニル共重合体、エチレン/酢
酸ビニル共重合体、エチレン/ビニルアルコール共重合
体、ポリビニルアルコール、ビニロン等のビニル重合
体、三酢酸セルロース、セロファン等のセルロース系樹
脂、ポリメタクリル酸メチル、ポリメタクリル酸エチ
ル、ポリアクリル酸エチル、ポリアクリル酸ブチル等の
アクリル系樹脂、ポリエーテルサルホン、ポリフェニレ
ンエーテル、ポリスチレン、ポリカーボネート、ポリア
リレート、ポリイミド等の合成樹脂フィルム又はシート
の単層体又は複数の積層体等が挙げられる。As the releasable substrate 2, a substrate film of about 5 to 200 μm having good releasability from the transfer layer 6 (release layer 3B) is used. Examples of the material of such a base film include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and a copolymer of polyethylene terephthalate / isophthalate; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; polyvinyl fluoride; and polyvinylidene fluoride. , Polytetrafluoroethylene, ethylene 4
Polyfluorinated ethylene resin such as fluorinated ethylene copolymer, polyamide polyvinyl chloride such as nylon 6 and nylon 66, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer , Polyvinyl alcohol, vinyl polymers such as vinylon, cellulose resins such as cellulose triacetate, cellophane, acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, and polyether sal A single layer or a plurality of layers of a synthetic resin film or sheet such as a phone, polyphenylene ether, polystyrene, polycarbonate, polyarylate, and polyimide are exemplified.
本発明転写箔の剥離性基材2は基材フィルム単独で用
いてもよいが、第1図に示すように必要に応じて転写層
6と剥離性基材2の離型性を促進するために基材フィル
ム21とその表面に設けた離型層22とから構成することも
できる。離型層8としては、フッ素系樹脂、各種ワック
ス、シリコーン等の離型剤をアクリル系樹脂、繊維素系
樹脂、ビニル系樹脂等のベヒクルに添加した塗膜を形成
したり、フッ素樹脂、シリコーン、メラミン系樹脂、ポ
リオレフィン樹脂、電離放射線架橋型の多官能アクリレ
ート、ポリエステル、エポキシ等の樹脂を塗工もしくは
エクストルージョンコート等で製膜したものを用いる。The release substrate 2 of the transfer foil of the present invention may be used alone as the substrate film, but as shown in FIG. 1, in order to promote the releasability of the transfer layer 6 and the release substrate 2 as necessary. And a release film 22 provided on the surface thereof. As the release layer 8, a coating film in which a release agent such as a fluororesin, various waxes, and silicone is added to a vehicle such as an acrylic resin, a cellulose resin, and a vinyl resin, or a fluororesin or silicone And a resin such as a melamine-based resin, a polyolefin resin, or an ionizing radiation-crosslinkable polyfunctional acrylate, polyester, or epoxy resin formed by coating or extrusion coating.
またインモールド転写箔(成型同時転写用転写箔)と
して使用する場合の離型層は、成型時の耐熱性、可撓
性、剥離層との経時安定性等を考慮して、アクリル、メ
ラミン、ウレタン、ポリエステル、アミノアルキッド、
エポキシ、等の熱硬化性樹脂単体、あるいはそれら2種
以上の混合物を用いるのが好ましく、更にこのインモー
ルド転写箔用の離型層には、必要に応じて転写層との離
型性を調節するためにシリコーン、フッ素樹脂、パラフ
ィン等の離型剤を添加することもできる。In addition, when used as an in-mold transfer foil (transfer foil for simultaneous transfer of molding), the release layer is made of acrylic, melamine, or the like in consideration of heat resistance at the time of molding, flexibility, and stability over time with a release layer. Urethane, polyester, amino alkyd,
It is preferable to use a single thermosetting resin such as epoxy, or a mixture of two or more of them. Further, the release layer for the in-mold transfer foil may be adjusted to have a release property with the transfer layer as necessary. For this purpose, a release agent such as silicone, fluororesin or paraffin can be added.
装飾層としては絵柄層4以外にも、例えば第2図に示
すように金属蒸着層8を設けることができる。これらの
装飾層4は、全面に設けても部分的に設けても良く、絵
柄層4の模様としては木目、石目、布目等の天然物の意
匠、文字、図形、記号、各種抽象模様等のいずれでもよ
い。As the decorative layer, in addition to the picture layer 4, for example, a metal deposition layer 8 can be provided as shown in FIG. The decorative layer 4 may be provided on the entire surface or partially. The pattern of the picture layer 4 may be a natural product such as wood grain, stone grain, cloth grain, letters, figures, symbols, various abstract patterns, etc. Either may be used.
この絵柄層4を形成するインキとしてはベヒクルに必
要に応じて、顔料、染料等の着色剤、体質顔料、溶剤、
安定剤、可塑剤、触媒、硬化剤等を適宜混合したものを
用いる。上記ベヒクルとしては、熱可塑性樹脂、熱硬化
性樹脂、電離放射線硬化性樹脂等の中から用途、必要な
物性、印刷適性等に応じて適宜選択する。上記ベヒクル
に用いる熱可塑性樹脂としては、上記の剥離層に用いる
熱可塑性樹脂と同様の樹脂を用いることができる。The ink for forming the picture layer 4 may include a pigment, a coloring agent such as a dye, an extender pigment, a solvent,
A material obtained by appropriately mixing a stabilizer, a plasticizer, a catalyst, a curing agent, and the like is used. The vehicle is appropriately selected from a thermoplastic resin, a thermosetting resin, an ionizing radiation-curable resin, and the like according to the use, necessary physical properties, printability, and the like. As the thermoplastic resin used for the vehicle, the same resin as the thermoplastic resin used for the release layer can be used.
金属属蒸着層9は、真空蒸着やスパッタリング等で形
成される金属薄膜層であり、金属としては通常上記の方
法で使用される金属が使用可能であり、例えば銅、ニッ
ケル、コバルト、クロム、アルミニウム、銀、亜鉛、又
は黄銅、ステンレス等の合金が挙げられる。また金属蒸
着層9は400〜4000Å程度の厚さに形成することが好ま
しく、転写箔の表面全面に設けてもよいが、部分的に設
けることもできる。金属蒸着層を部分的に設ける場合、
次のように行うことができる。The metal-deposited layer 9 is a metal thin film layer formed by vacuum deposition, sputtering, or the like. As the metal, a metal usually used in the above method can be used. For example, copper, nickel, cobalt, chromium, aluminum , Silver, zinc, or alloys such as brass and stainless steel. The metal deposition layer 9 is preferably formed to a thickness of about 400 to 4000 °, and may be provided on the entire surface of the transfer foil, or may be provided partially. When partially providing a metal deposition layer,
It can be performed as follows.
まず蒸着不要部分にポリビニルアルコール、セルロー
ス系樹脂、デンプン等の水溶性樹脂からなる除去層を設
けた後、この除去層全面に金属蒸着を施す。次いで水洗
して水溶性樹脂とともに、この水溶性樹脂の上面側の蒸
着層を除去する。あるいは全面に蒸着を施した後に部分
蒸着層として残す必要がある部分の上面に保護層を設け
次いで酸、アルカリ等により蒸着不要部分を溶解除去す
る方法等により形成する。First, after a removal layer made of a water-soluble resin such as polyvinyl alcohol, a cellulose-based resin, or starch is provided on a portion not requiring deposition, metal deposition is performed on the entire surface of the removal layer. Next, the substrate is washed with water to remove the vapor-deposited layer on the upper surface side of the water-soluble resin together with the water-soluble resin. Alternatively, a protective layer is provided on an upper surface of a portion that needs to be left as a partial vapor deposition layer after vapor deposition is performed on the entire surface, and then a portion unnecessary for vapor deposition is dissolved and removed with an acid, an alkali, or the like.
本発明では、蒸着安定層10を金属蒸着層8の剥離性基
材2側に設けることができる。蒸着安定層10は、耐熱
性、密着性等に優れたものが用いられ、このような材質
として例えば1液型又は2液型のポリウレタン、ポリア
ミド、ポリイミド、ポリアクリル酸誘導体、ポリエステ
ル等の樹脂が挙げられる。蒸着安定層10を設けることに
よって、金属蒸着層8と各層との間の密着性がより向上
する。In the present invention, the vapor deposition stable layer 10 can be provided on the side of the releasable substrate 2 of the metal vapor deposition layer 8. As the vapor deposition stabilizing layer 10, a material having excellent heat resistance, adhesion and the like is used. For example, a resin such as one-pack or two-pack polyurethane, polyamide, polyimide, polyacrylic acid derivative, or polyester is used as such a material. No. By providing the deposition stable layer 10, the adhesion between the metal deposition layer 8 and each layer is further improved.
また本発明転写箔は第2図に示すように、接着剤層5
と金属蒸着層8等の装飾層との間にプライマー層9を設
けることができる。プライマー層9を設けることによ
り、接着剤層5と装飾層8の間の密着性がより向上す
る。Further, as shown in FIG. 2, the transfer foil of the present invention has an adhesive layer 5
A primer layer 9 can be provided between the metal layer 8 and a decorative layer such as the metal deposition layer 8. By providing the primer layer 9, the adhesion between the adhesive layer 5 and the decoration layer 8 is further improved.
本発明転写箔の使用にあたっては、第3図に示す如
く、被転写体11に転写箔の接着剤層5が被転写体11の表
面と接するように重ね合わせて、必要に応じ加圧もしく
は加熱等を加えた後に、剥離性基材を剥離して被転写体
11に転写層6を転移することができる。When using the transfer foil of the present invention, as shown in FIG. 3, the adhesive layer 5 of the transfer foil is superimposed on the transfer object 11 so as to be in contact with the surface of the transfer object 11, and the pressure or heat is applied as necessary. After the addition of the transfer material
The transfer layer 6 can be transferred to 11.
本発明の転写箔は、射出成型と同時に転写を行う射出
成型同時転写、熱転写、溶剤活性転写等の種々の方法に
用いることができる。特に本発明の転写箔は射出成型同
時転写のような曲面等の複雑な形状に転写を行う場合の
転写箔として最適に用いることができる。The transfer foil of the present invention can be used in various methods such as simultaneous injection molding transfer, thermal transfer, and solvent activated transfer in which transfer is performed simultaneously with injection molding. In particular, the transfer foil of the present invention can be optimally used as a transfer foil when performing transfer to a complicated shape such as a curved surface such as simultaneous transfer by injection molding.
次に、具体的実施例を挙げて本発明を更に詳細に説明
する。Next, the present invention will be described in more detail with reference to specific examples.
実施例1 アクリルメラミン離型層を有する厚さ38μmのポリエ
チレンテレフタレートフィルム(ダイアホイル(株)
製:GH38)の離型層側表面に、アクリル系ビヒクルと数
平均分子量が約5000で鱗片状のポリエチレンワックスを
ビヒクルに対して4重量%添加したハクリインキ
((株)昭和インク工業所製:ハクリニス46H4%)をグ
ラビア印刷にて塗布量1.5g/m2になるように塗工して剥
離層Bを形成した。次いで、剥離層Bの表面に更にアク
リル系ビヒクルと数平均分子量が約2000で塊状のポリエ
チレンワックスをビヒクルに対して2重量%添加したハ
クリインキ((株)昭和インク工業所製:ハクリニス64
L2%)をグラビア印刷にて塗布量1.5g/m2になるように
塗工して剥離層Aを形成した。剥離層Aの表面側に透明
部が形成されるようにパターン状に絵柄層((株)昭和
インク工業所製:BCT)、接着剤層((株)昭和インク工
業所製:HSAS11)グラビア印刷にて形成して本発明転写
箔を得た。Example 1 38 μm-thick polyethylene terephthalate film having an acrylic melamine release layer (Diafoil Co., Ltd.)
Acrylic vehicle and flake-like polyethylene wax having a number average molecular weight of about 5000 and 4% by weight of 4% by weight of the vehicle were added to the release layer side surface of GH38) (Hakurinis, manufactured by Showa Ink Industries, Ltd.). 46H4%) was applied by gravure printing to a coating amount of 1.5 g / m 2 to form a release layer B. Next, an acrylic vehicle and a bulk polyethylene wax having a number average molecular weight of about 2000 and 2 mass% of 2% by weight based on the vehicle were added to the surface of the release layer B. Hakuri ink 64 (manufactured by Showa Ink Industry Co., Ltd .: Hakurinis 64)
L2%) was applied by gravure printing to a coating amount of 1.5 g / m 2 to form a release layer A. Gravure printing with a pattern layer (BCT, manufactured by Showa Ink Industries, Ltd.) and an adhesive layer (HSAS11, manufactured by Showa Ink Industries, Ltd.) in a pattern so that a transparent portion is formed on the surface side of the release layer A. To obtain a transfer foil of the present invention.
得られた転写箔を射出成型金型内部に接着剤層と成型
樹脂が接するようにに載置して、ASクリアー樹脂を溶融
樹脂としてインモールド成型を行い転写を行い、透明性
に優れた剥離層を有する成型品を得た。成型品表面の剥
離層の耐摩耗性、ヘイズ値について試験を行った結果を
表1に示す。表1に示すように、ヘイズ値は4.3%、RCA
耐摩耗性は60と良好な値を示していた。The resulting transfer foil is placed inside the injection mold so that the adhesive layer and the molding resin are in contact with each other. A molded article having a layer was obtained. Table 1 shows the results of tests performed on the wear resistance and haze value of the release layer on the surface of the molded product. As shown in Table 1, the haze value was 4.3%, RCA
The abrasion resistance showed a good value of 60.
参考例 実施例1の剥離層Bの代わりに剥離層Aを用いて剥離
層Aを2層重ねて剥離層を形成した以外は実施例1と全
く同様にして転写箔を形成して、インモールド転写を行
った。成型品表面の剥離層の耐摩耗性、ヘイズ値につい
て試験を行った結果を表1に示す。Reference Example A transfer foil was formed in exactly the same manner as in Example 1 except that the release layer A was used instead of the release layer B in Example 1 and two release layers A were stacked to form a release layer. Transfer was performed. Table 1 shows the results of tests performed on the wear resistance and haze value of the release layer on the surface of the molded product.
実施例2 アクリルメラミン離型層を有する厚さ38μmのポリエ
チレンテレフタレートフィルム(ダイアホイル(株):G
H38)の離型層側表面に、実施例1と同様に剥離層Bと
剥離層Aを順次形成した。Example 2 A 38 μm-thick polyethylene terephthalate film having an acrylic melamine release layer (Diafoil Co., Ltd .: G
A release layer B and a release layer A were sequentially formed on the release layer side surface of H38) in the same manner as in Example 1.
次いで、剥離層Aの表面側に透明部が形成されるよう
にパターン状に絵柄層((株)昭和インク工業所製:BC
T)を部分的に設け、その上に蒸着安定層((株)昭和
インク工業所製:AC No.8、硬化剤20部)グラビア印刷に
て全面に設け、その後蒸着不要部分に水洗プライマー
((株)昭和インク工業所製:HS32G)を塗工して60℃で
3日間養生し、その表面全体にアルミニウム蒸着を施し
た後水洗プライマー層を水洗乾燥し蒸着不要部分を除去
した後像着層側に全面に接着プライマー層((株)昭和
インク工業所製:水洗プライマーNo.4)、接着剤層
((株)昭和インク工業所製:HSAS11)を順次設けて部
分蒸着層を有する転写箔を得た。Next, a pattern layer (BC manufactured by Showa Ink Industries, Ltd .: BC) is formed in a pattern so that a transparent portion is formed on the surface side of the release layer A.
T) is partially provided, and a vapor deposition stabilizing layer (Showa Ink Kogyo Co., Ltd .: AC No. 8, 20 parts of curing agent) is provided over the entire surface by gravure printing. Coated with Showa Ink Industries Co., Ltd .: HS32G), cured at 60 ° C for 3 days, coated with aluminum on the entire surface, washed and dried with a rinse primer layer to remove unnecessary deposits, and then imaged. An adhesive primer layer (manufactured by Showa Ink Kogyo Co., Ltd .: Rinse No.4) and an adhesive layer (Hitachi Showa Ink Kogyo Co., Ltd .: HSAS11) are sequentially provided on the entire surface of the layer to transfer a partially vapor-deposited layer. A foil was obtained.
得られた転写箔を実施例1と同様にインモールド成型
を行って実際の転写を行ったところ蒸着部に曇りのない
透明性に優れた剥離層を有する成型品が得られた。また
実施例1と同様にヘイズ値、耐摩耗性試験を行い、試験
結果を表1に示す。The obtained transfer foil was subjected to in-mold molding and actual transfer in the same manner as in Example 1. As a result, a molded product having a cloudy and highly transparent release layer without fogging was obtained in the deposited portion. Further, a haze value and a wear resistance test were performed in the same manner as in Example 1, and the test results are shown in Table 1.
比較例1 比較のために、剥離層をアクリル系ビヒクルと数平均
分子量が2000〜3000で花弁状のポリエチレンワックスを
ビヒクルに対して5重量%添加したハクリニス((株)
昭和インク工業所製:ハクリニス46)をグラビア印刷に
て塗布量1.5g/m2になるように塗工して設けた剥離層C
と該剥離層Cの表面に更に同じ剥離層Cを1.5g/m2にな
るように塗工して設けた剥離層とから形成した以外は、
全て実施例1と同様にして転写箔を製造し、インモール
ド転写を行った。COMPARATIVE EXAMPLE 1 For comparison, Haklinis (available from Co., Ltd.) in which a release layer was added to an acrylic vehicle and petal-like polyethylene wax having a number average molecular weight of 2,000 to 3,000 and 5% by weight based on the vehicle.
Release layer C formed by applying Showa Ink Industries Co., Ltd .: Haklinis 46) by gravure printing to a coating amount of 1.5 g / m 2.
And a release layer further provided on the surface of the release layer C by applying the same release layer C to 1.5 g / m 2 .
A transfer foil was manufactured in the same manner as in Example 1, and in-mold transfer was performed.
成型品へ転写した転写箔の転写層は透明部が曇ってい
て剥離層の下層の絵柄が鮮明に見えなかった。実施例1
と同様にヘイズ値、耐摩耗性試験を行い、試験結果を表
1に示す。In the transfer layer of the transfer foil transferred to the molded product, the transparent portion was cloudy, and the pattern below the release layer was not clearly visible. Example 1
A haze value and a wear resistance test were performed in the same manner as in Example 1. Table 1 shows the test results.
比較例2 実施例2の剥離層をアクリル系ビヒクルと数平均分子
量が2000〜3000で花弁状のポリエチレンワックスをビヒ
クルに対して5重量%添加したハクリニス((株)昭和
インク工業所製:ハクリニス46)をグラビア印刷にて塗
布量1.5g/m2になるように塗工して設けた剥離層Aと該
剥離層Aの表面に更に同じ剥離層Aを1.5g/m2になるよ
うに塗工して設けた剥離層とから形成した以外は、全て
実施例3と同様にして転写箔を製造し、インモールド転
写を行った。Comparative Example 2 Haklinis 46 (manufactured by Showa Ink Industry Co., Ltd.) in which the release layer of Example 2 was an acrylic vehicle and petal-like polyethylene wax having a number average molecular weight of 2,000 to 3,000 and 5% by weight of the vehicle were added to the vehicle. coating further same release layer a on the surface of the coating weight 1.5 g / release layer is provided by coating so as m becomes 2 a and the release layer a to be 1.5 g / m 2 a) by gravure printing A transfer foil was manufactured and in-mold transfer was performed in the same manner as in Example 3 except that the transfer foil was formed from an exfoliated layer provided by machining.
成型品へ転写した転写箔の転写層は透明部が曇ってい
て剥離層の下層の蒸着層が鮮明に見えなかった。実施例
1と同様にヘイズ値、耐摩耗性試験を行い、試験結果を
表1に示す。In the transfer layer of the transfer foil transferred to the molded product, the transparent portion was cloudy, and the deposited layer below the release layer was not clearly visible. A haze value and a wear resistance test were performed in the same manner as in Example 1, and the test results are shown in Table 1.
〔発明の効果〕 以上説明したように、本発明は剥離層を2層以上から
形成し、少なくとも最も剥離性基材側に設けた剥離層に
ワックスを含有せしめ、且つ最も装飾層側に設けた剥離
層をヘイズ値が単層で5%以下になるように形成した構
成を採用したことにより、従来の剥離層に単にワックス
を添加した一つの剥離層のみからなる転写箔や、剥離層
の剥離層の厚みを厚くしただけの転写箔に比較して、ワ
ックスを剥離層の剥離性基材側(即ち転写後の最表面と
なる層)に添加して耐摩耗性をこの剥離層に持たせ、装
飾層側(即ち転写層の表面にでない部分)に設けた剥離
層に透明性を持たせることで、剥離層の透明性を損なわ
ずに耐摩耗性を向上させることが可能となり、被転写体
に転写層を転写した際に剥離層の透明性に優れ、装飾層
の意匠が鮮明に見えるという優れた意匠性を有し、且つ
転写層表面の耐摩耗性が良好な効果を有する。 [Effects of the Invention] As described above, in the present invention, a release layer is formed from two or more layers, at least the release layer provided on the releasable base material side contains wax, and the release layer is provided on the decoration layer side. By adopting a configuration in which the release layer is formed such that the haze value is 5% or less in a single layer, a transfer foil consisting of only a single release layer obtained by simply adding wax to a conventional release layer, or the release of the release layer Compared with the transfer foil having only a thicker layer, wax is added to the release substrate side of the release layer (that is, the layer which is the outermost surface after transfer) to give the release layer abrasion resistance. By imparting transparency to the release layer provided on the decorative layer side (that is, a portion that is not on the surface of the transfer layer), it is possible to improve abrasion resistance without impairing the transparency of the release layer. When the transfer layer is transferred to the body, the release layer has excellent transparency, It has excellent design properties such that the design looks sharp, and has a good effect on the abrasion resistance of the transfer layer surface.
また上記の剥離層のワックスの含有量を最も剥離性基
材側の剥離層から装飾層の剥離層に行くに従って順次減
少するように設けた場合、各剥離層の間のワックスの濃
度差が小さくなるために密着性が不良となる虞れがなく
優れた剥離層を形成することが可能である。Further, when the wax content of the release layer is provided so as to gradually decrease from the release layer on the side of the most releasable substrate to the release layer of the decorative layer, the difference in the concentration of wax between the release layers is small. Therefore, it is possible to form an excellent release layer without the risk of poor adhesion.
また本発明は最も剥離性基材側の剥離層に数平均分子
量が1000〜8000で、形状が花弁状あるいは鱗片状のポリ
エチレンワックスを含有せしめることにより、より耐摩
耗性に優れた転写箔を得ることができる。In addition, the present invention provides a transfer foil having more excellent wear resistance by allowing the release layer on the most releasable substrate side to have a number average molecular weight of 1,000 to 8,000 and containing a petal-like or flaky polyethylene wax in shape. be able to.
更に、最も装飾層側の剥離層に数平均分子量が500〜3
000で、形状が塊状のポリエチレンワックスを含有せし
めた場合、透明性、耐摩耗性にとってより優れた転写箔
を得ることができ、装飾層に金属薄膜層を形成した場合
でも、透明性が良好であるために、金属薄膜層に曇り等
が見られず良好な転写箔を得ることができる。Furthermore, the number-average molecular weight of the release layer closest to the decoration layer is 500 to 3
000, when the shape contains a massive polyethylene wax, transparency, it is possible to obtain a transfer foil more excellent in abrasion resistance, even when a metal thin film layer is formed on the decorative layer, the transparency is good For this reason, it is possible to obtain a good transfer foil without fogging or the like in the metal thin film layer.
第1図は本発明転写箔の一実施例を示す縦断面略図、第
2図は本発明転写箔の他の例を示す縦断面略図、第3図
は本発明転写箔の使用例を示す縦断面略図である。 1……転写箔、2……剥離性基材、3……剥離層、3A…
…装飾層側の剥離層、3B……剥離性基材側の剥離層、4
……絵柄層、6……離型層FIG. 1 is a schematic longitudinal sectional view showing one embodiment of the transfer foil of the present invention, FIG. 2 is a schematic longitudinal sectional view showing another example of the transfer foil of the present invention, and FIG. FIG. 1 ... transfer foil, 2 ... peelable substrate, 3 ... release layer, 3A ...
... release layer on decorative layer side, 3B ... release layer on release substrate side, 4
…… Pattern layer, 6 …… Release layer
Claims (2)
層、装飾層を順次積層してなる転写箔において、上記剥
離層を2層以上から形成し、最も剥離性基材側に設けた
剥離層に、数平均分子量が1000〜8000で形状が花弁状あ
るいは鱗片状のポリエチレンワックスを含有せしめ、且
つ最も装飾層側の剥離層に、数平均分子量が500〜3000
で形状が塊状のポリエチレンワックスを含有せしめ該剥
離層のヘイズ値が単層で5%以下になるように形成した
ことを特徴とする転写箔。1. A transfer foil comprising a release layer having a transparent portion on the surface of a peelable substrate and a decorative layer sequentially laminated, wherein the release layer is formed from two or more layers and provided on the peelable substrate side most. The release layer has a number-average molecular weight of 1000 to 8000 and the shape contains petal-like or flaky polyethylene wax, and the release layer closest to the decoration layer has a number-average molecular weight of 500 to 3000.
A transfer foil, characterized in that the transfer foil is formed so that a single layer of the release layer has a haze value of 5% or less.
材側の剥離層から装飾層側の剥離層に行くに従って順次
減少するように設けた請求項1記載の転写箔。2. The transfer foil according to claim 1, wherein the wax content of the release layer is provided so as to gradually decrease from the release layer on the release substrate side to the release layer on the decoration layer side.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2280237A JP3006866B2 (en) | 1990-10-18 | 1990-10-18 | Transfer foil |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2280237A JP3006866B2 (en) | 1990-10-18 | 1990-10-18 | Transfer foil |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04153100A JPH04153100A (en) | 1992-05-26 |
JP3006866B2 true JP3006866B2 (en) | 2000-02-07 |
Family
ID=17622214
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2280237A Expired - Lifetime JP3006866B2 (en) | 1990-10-18 | 1990-10-18 | Transfer foil |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3006866B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4853852B2 (en) * | 2006-03-16 | 2012-01-11 | 東レフィルム加工株式会社 | Transfer foil |
JP6480583B2 (en) * | 2014-08-05 | 2019-03-13 | ユニカルタ・インコーポレイテッド | Construction of ultra-small or ultra-thin discrete components that are easy to assemble |
-
1990
- 1990-10-18 JP JP2280237A patent/JP3006866B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH04153100A (en) | 1992-05-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101048714B1 (en) | Three-dimensional transfer sheet | |
JP3851523B2 (en) | Metal gloss sheet for 3D molding | |
US4687680A (en) | Stamping foil | |
JPH04301491A (en) | Mold release sheet and transfer sheet | |
JP6205786B2 (en) | Transfer foil for producing a hydraulic transfer film, method for producing a hydraulic transfer film, and method for producing a decorative molded product | |
JP3006866B2 (en) | Transfer foil | |
JP2004299384A (en) | Decorative sheet with protecting sheet and method for manufacturing decorative molding | |
JPH05124394A (en) | Leather expression transfer foil | |
JP2571401B2 (en) | Metallic gloss sheet with excellent moldability | |
JPH0825789A (en) | Transfer sheet | |
JP2964590B2 (en) | Release paper | |
JP6264484B2 (en) | Hydraulic transfer film | |
JPH0745279B2 (en) | Transfer foil | |
JPS6123440Y2 (en) | ||
JP4248230B2 (en) | Metal surface decorative material and insert molded product using the same | |
JPH0241440B2 (en) | ||
JP2524810B2 (en) | Transcription sheet | |
JP3011442B2 (en) | Injection molding simultaneous transfer method | |
JP2018158578A (en) | Water pressure transfer film | |
JPH08142598A (en) | Metallic gloss transfer foil with formability | |
JPS5919834B2 (en) | Transfer foil base material | |
JPH05177992A (en) | Transfer foil for simultaneous transfer and injection molding | |
JP3414722B2 (en) | Decorative members and decorative sheets | |
JPH02310051A (en) | Transfer sheet for forming pattern having three-dimensional feeling | |
JP2004299091A (en) | Decorative sheet and method for manufacturing decorative molded product |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071126 Year of fee payment: 8 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081126 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081126 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091126 Year of fee payment: 10 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091126 Year of fee payment: 10 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101126 Year of fee payment: 11 |
|
EXPY | Cancellation because of completion of term |