JP6205786B2 - Transfer foil for producing a hydraulic transfer film, method for producing a hydraulic transfer film, and method for producing a decorative molded product - Google Patents
Transfer foil for producing a hydraulic transfer film, method for producing a hydraulic transfer film, and method for producing a decorative molded product Download PDFInfo
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- JP6205786B2 JP6205786B2 JP2013070639A JP2013070639A JP6205786B2 JP 6205786 B2 JP6205786 B2 JP 6205786B2 JP 2013070639 A JP2013070639 A JP 2013070639A JP 2013070639 A JP2013070639 A JP 2013070639A JP 6205786 B2 JP6205786 B2 JP 6205786B2
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- resin
- film
- layer
- water
- hydraulic transfer
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Images
Landscapes
- Decoration By Transfer Pictures (AREA)
- Laminated Bodies (AREA)
Description
本発明は、水圧転写フィルム製造用転写箔、及び水圧転写フィルムに関する。 The present invention relates to a transfer foil for producing a hydraulic transfer film and a hydraulic transfer film.
建材や、自動車内装品、家電製品又はＯＡ機器などには表面に木目調や金属調（金属光沢）などの装飾が施された成型品が利用されている。これらの成型品は複雑な三次元形状を有するものが多く、従来、その複雑な形状からなる成型品に意匠性の高い装飾を簡便に施す方法が検討されている。
こうした装飾方法として、水圧を利用した水圧転写法が知られており、この水圧転写法は、立体面への転写加工性、クリア塗装感などの「深み」や、高品質な柄表現が出来るなどの意匠性の点で、優れた曲面加飾法であることが知られている。
For building materials, automobile interior products, home appliances, OA equipment, etc., molded products having decorations such as wood grain or metallic tone (metallic luster) on the surface are used. Many of these molded products have a complicated three-dimensional shape, and conventionally, a method of simply applying a highly designed decoration to a molded product having the complicated shape has been studied.
As such a decoration method, a water pressure transfer method using water pressure is known. This water pressure transfer method can perform transfer processing to a three-dimensional surface, “depth” such as a clear paint feeling, and high quality pattern expression. It is known that it is an excellent curved surface decorating method in terms of design properties.
近年の需要者の意匠性への要求が厳しくなっており、とりわけ金属調（金属光沢）の装飾において、光輝性の高さに加えて高級感が求められるようになっている。このような課題に対して、例えば、光輝性を発現する層とエンボス加工による凹凸形状とにより解決する手法、具体的には、水溶性フィルム上の硝化綿・アルキッド系の透明樹脂層と、該透明樹脂層上の蒸着金属層とからなり、該蒸着金属層と前記透明樹脂層との間で該透明樹脂層にエンボスが施された水圧転写フィルムが提案されている（例えば、特許文献１）。 In recent years, the demand for design by consumers has become strict, and in particular, in the decoration of metallic tone (metallic luster), a high-class feeling has been demanded in addition to high glitter. For such a problem, for example, a method for solving the problem by a layer exhibiting glitter and an uneven shape by embossing, specifically, a nitrified cotton / alkyd transparent resin layer on a water-soluble film, There has been proposed a hydraulic transfer film comprising a vapor-deposited metal layer on a transparent resin layer and having the transparent resin layer embossed between the vapor-deposited metal layer and the transparent resin layer (for example, Patent Document 1). .
特許文献１に記載される水圧転写フィルムを用いると、水圧転写時にシートが伸展する際に、蒸着金属層に微細なクラック（割れ）が生じることで蒸着金属層も伸展し、曲面転写をすることが可能となる。しかし、水圧転写時の蒸着金属層に発生するクラック幅の大小により意匠性に大きな差異が生じてしまい、またクラック幅が広いと柄の高級感が損なわれるといった問題があった。 When the hydraulic transfer film described in Patent Document 1 is used, when the sheet is stretched during hydraulic transfer, the vapor deposited metal layer is also stretched due to the occurrence of fine cracks in the vapor deposited metal layer, and the curved surface is transferred. Is possible. However, there is a problem in that a large difference in design is caused by the size of the crack width generated in the vapor deposition metal layer at the time of hydraulic transfer, and the high-quality feeling of the pattern is impaired when the crack width is wide.
ところで、水圧転写フィルムの基材としては、特許文献１でも用いられているように、ポリビニルアルコール樹脂フィルムを代表とする水溶性フィルムが一般的に用いられてきた。しかし、ポリビニルアルコール樹脂フィルムは熱に弱く、水圧転写フィルムに凹凸形状を付与するエンボス加工の際に、凹凸形状を十分に付与できず、光輝性と高級感とを備える意匠性が得られないという問題があった。さらに、水溶性を有する樹脂フィルムを基材として用いると、例えば、水圧転写フィルムを長期保管した場合に、空気中の水分を吸収してカーリングやブロッキングを生じやすく、また、空気中の湿度の影響でフィルムが伸縮することで、装飾層の意匠に悪影響を与えるという問題もあった。 By the way, as a base material of a hydraulic transfer film, as used in Patent Document 1, a water-soluble film represented by a polyvinyl alcohol resin film has been generally used. However, the polyvinyl alcohol resin film is vulnerable to heat, and when embossing for imparting a concavo-convex shape to a hydraulic transfer film, the concavo-convex shape cannot be sufficiently imparted, and a design property with glitter and luxury cannot be obtained. There was a problem. In addition, when a water-soluble resin film is used as a base material, for example, when a hydraulic transfer film is stored for a long period of time, it easily absorbs moisture in the air and causes curling and blocking, and the influence of humidity in the air There was also a problem that the design of the decorative layer was adversely affected by the expansion and contraction of the film.
そこで、耐熱性に優れる基材としてポリエチレンテレフタレート樹脂（ＰＥＴ樹脂）フィルムを採用し、該基材に金属薄膜層などからなる加飾層などを設け、エンボス加工を施して凹凸形状を形成した転写箔を用いて水圧転写フィルムを作製することで、凹凸形状を十分に付与できないという問題を解決する方法が提案されている（例えば、特許文献２）。この方法により、水圧転写フィルムは十分な凹凸形状を有するものとなった。しかしながら、特許文献１に記載の水圧転写フィルムと同様に、水圧転写時において、蒸着金属で形成された金属薄膜層に生じるクラック幅の大小によって意匠性に差が生じるなどの問題については、依然として解消されていなかった。 Therefore, a transfer foil in which a polyethylene terephthalate resin (PET resin) film is used as a base material having excellent heat resistance, a decorative layer made of a metal thin film layer or the like is provided on the base material, and embossing is performed to form an uneven shape. There has been proposed a method for solving the problem that a concave-convex shape cannot be sufficiently imparted by producing a hydraulic transfer film using a film (for example, Patent Document 2). By this method, the hydraulic transfer film has a sufficient uneven shape. However, as with the hydraulic transfer film described in Patent Document 1, problems such as differences in design properties due to the size of the crack width generated in the metal thin film layer formed of vapor-deposited metal are still solved during hydraulic transfer. Was not.
特許文献１や２において、光輝性と高級感とを備える意匠性を得るため、蒸着金属層に代えて、光輝性インキ層とし、該光輝性インキ層に凹凸形状を設けることを検討した。しかし、水圧転写時に光輝性インキ層が伸展しすぎてしまい、凹凸感が消失してしまったため、優れた光輝性と高級感とを備える意匠性を得ることはできなかった。これは、特許文献２に記載の方法を用いることで、水圧転写フィルムに十分な凹凸形状を賦型した場合においても同様であった。
さらに、光輝性インキ層の凹凸形状を保持して凹凸感の消失を防止するために、水圧転写フィルムの基材である水溶性フィルムと光輝性インキ層との間に樹脂層を設け、光輝性インキ層の過度な伸展を抑制することを検討した。しかし、当該樹脂層を形成する樹脂の種類によっては、水圧転写フィルムの製造時に光輝性インキ層が剥がれてしまうなど、該光輝性インキ層に良好な凹凸形状を賦型することができず、光輝性や高級感が損なわれる場合があった。
本発明は、このような状況下で、転写箔の製造時に凹凸形状が良好に賦型されており、かつ優れた光輝性と高級感とを備える意匠性を樹脂成形品に付与しうる水圧転写フィルムの製造に適した水圧転写フィルム製造用転写箔、水圧転写フィルム、転写箔を用いた水圧転写フィルムの製造方法、及び該フィルムを用いた加飾成形品を提供することを課題とする。
In Patent Documents 1 and 2, in order to obtain a design with a glitter and a high-class feeling, it was considered that a glitter ink layer was used instead of the vapor-deposited metal layer, and an uneven shape was provided on the glitter ink layer. However, since the glittering ink layer was excessively extended during the hydraulic transfer and the unevenness disappeared, it was not possible to obtain a design with excellent glitter and luxury. This was the same even when a sufficient uneven shape was formed on the hydraulic transfer film by using the method described in Patent Document 2.
Furthermore, in order to maintain the uneven shape of the glitter ink layer and prevent the disappearance of the uneven feeling, a resin layer is provided between the water-soluble film, which is the base material of the hydraulic transfer film, and the glitter ink layer. It was studied to suppress excessive extension of the ink layer. However, depending on the type of resin that forms the resin layer, the glitter ink layer cannot be formed into a glittering ink layer, for example, the glitter ink layer may be peeled off during the production of a hydraulic transfer film. In some cases, the quality and the sense of quality were impaired.
Under such circumstances, the present invention provides a hydraulic transfer in which a concavo-convex shape is satisfactorily shaped at the time of manufacturing a transfer foil, and can impart design properties with excellent glitter and high-class feeling to a resin molded product. It is an object to provide a transfer foil for producing a hydraulic transfer film suitable for production of a film, a hydraulic transfer film, a method for producing a hydraulic transfer film using the transfer foil, and a decorative molded product using the film.
本発明者らは、前記課題を解決するために鋭意研究を重ねた結果、下記の発明により解決できることを見出した。すなわち本発明は、下記の水圧転写フィルム製造用転写箔、水圧転写フィルム、転写箔を用いた水圧転写フィルムの製造方法、及び該フィルムを用いた加飾成形品を提供するものである。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the problem can be solved by the following invention. That is, the present invention provides the following transfer foil for producing a hydraulic transfer film, a hydraulic transfer film, a method for producing a hydraulic transfer film using the transfer foil, and a decorative molded product using the film.
１．剥離フィルム、伸展抑制樹脂層、及び光輝性インキ層を順に有し、少なくとも該光輝性インキ層の伸展抑制樹脂層の側とは反対側の面に凹凸形状を有し、該伸展抑制樹脂層を形成する樹脂がガラス転移温度８０℃以上の樹脂Ａを含む水圧転写フィルム製造用転写箔。
２．水溶性フィルム、光輝性インキ層、及び伸展抑制樹脂層を順に有し、少なくとも該光輝性インキ層の伸展抑制樹脂層の側とは反対側の面に凹凸形状を有し、該伸展抑制樹脂層を形成する樹脂がガラス転移温度８０℃以上の樹脂Ａを含む水圧転写フィルム。
３．以下の工程（Ａ）〜（Ｃ）を順に有する、水溶性フィルム、光輝性インキ層、及びプライマー層を順に有する水圧転写フィルムの製造方法。
工程（Ａ）剥離フィルム、伸展抑制樹脂層、及び光輝性インキ層を順に有し、少なくとも該光輝性インキ層の伸展抑制樹脂層の側とは反対側の面に凹凸形状を有し、該伸展抑制樹脂層を形成する樹脂がガラス転移温度８０℃以上の樹脂Ａを含む水圧転写フィルム製造用転写箔の光輝性インキ層及び／又は水溶性フィルムに活性剤を塗布する工程
工程（Ｂ）該転写箔の光輝性インキ層側に該水溶性フィルムを積層する工程
工程（Ｃ）剥離フィルムを剥離する工程
４．下記の工程（ａ）〜（ｃ）を順に有する加飾成形品の製造方法。
工程（ａ）水溶性フィルム、光輝性インキ層、及び伸展抑制樹脂層を順に有し、少なくとも該光輝性インキ層の伸展抑制樹脂層の側とは反対側の面に凹凸形状を有し、該伸展抑制樹脂層を形成する樹脂がガラス転移温度８０℃以上の樹脂Ａを含む水圧転写フィルムを該水溶性フィルム側が水面側に向くように水面に浮遊させる前又は後に、該伸展抑制樹脂層に活性剤組成物を塗布する活性剤塗布工程
工程（ｂ）該工程（ａ）を経た水圧転写フィルム上に被転写体を押圧し、水圧によって該伸展抑制樹脂層を被転写体の被転写面に密着させる工程
工程（ｃ）該被転写体の被転写面に密着した水溶性フィルムを除去する脱膜工程
1. It has a release film, an extension suppressing resin layer, and a glittering ink layer in this order, and has an uneven shape on at least the surface of the glittering ink layer opposite to the extension suppressing resin layer, and the extension suppressing resin layer A transfer foil for producing a hydraulic transfer film, wherein the resin to be formed contains a resin A having a glass transition temperature of 80 ° C. or higher.
2. It has a water-soluble film, a glitter ink layer, and an extension suppressing resin layer in this order, and has an uneven shape on at least the surface of the glitter ink layer opposite to the extension suppressing resin layer, and the extension suppressing resin layer A hydraulic transfer film in which the resin forming the resin contains resin A having a glass transition temperature of 80 ° C. or higher.
3. The manufacturing method of the hydraulic transfer film which has the following process (A)-(C) in order, and has a water-soluble film, a glittering ink layer, and a primer layer in order.
Step (A) It has a release film, an extension suppressing resin layer, and a glittering ink layer in this order, and has an uneven shape on at least the surface of the glittering ink layer opposite to the extension suppressing resin layer. Step (B) of applying an activator to the glittering ink layer and / or water-soluble film of the transfer foil for producing a hydraulic transfer film, wherein the resin forming the suppression resin layer contains the resin A having a glass transition temperature of 80 ° C. or higher. 3. Step of laminating the water-soluble film on the glitter ink layer side of the foil (C) Step of peeling the release film The manufacturing method of the decorative molded product which has the following process (a)-(c) in order.
The step (a) has a water-soluble film, a glitter ink layer, and an extension suppressing resin layer in order, and has an uneven shape on at least the surface of the glitter ink layer opposite to the extension suppression resin layer, Before or after the hydraulic transfer film containing the resin A containing the resin A having a glass transition temperature of 80 ° C. or higher is floated on the water surface so that the water-soluble film side faces the water surface, the stretch-inhibiting resin layer is active in the stretch-inhibiting resin layer. Activator application step of applying the agent composition (b) The transferred object is pressed onto the hydraulic transfer film that has undergone the step (a), and the extension suppressing resin layer is brought into close contact with the transferred surface of the transferred object by water pressure. (C) film removal process for removing the water-soluble film adhered to the transfer surface of the transfer object
本発明の水圧転写フィルム製造用転写箔は、転写箔の製造時に凹凸形状が良好に賦型されており、かつ水圧転写フィルムを使用する前に簡単に水圧転写フィルムを作製することができる。本発明の転写箔を用いて得られる水圧転写フィルムは、良好な凹凸形状を有しており、かつ優れた光輝性と高級感とを備える意匠性を樹脂成形品に付与することができる。 The transfer foil for producing a hydraulic transfer film of the present invention has a well-shaped uneven shape at the time of producing the transfer foil, and the hydraulic transfer film can be easily produced before using the hydraulic transfer film. The hydraulic transfer film obtained by using the transfer foil of the present invention has a good concavo-convex shape, and can impart design properties with excellent glitter and high-class feeling to a resin molded product.
〔水圧転写フィルム製造用転写箔〕
以下、本発明の水圧転写フィルム製造用転写箔を図面に基づいて説明する。図１は、本発明の水圧転写フィルム製造用転写箔の構成の一例を示す概略断面図である。
本発明の水圧転写フィルム製造用転写箔１０は、剥離フィルム１１、伸展抑制樹脂層１２、及び光輝性インキ層１３を順に有し、少なくとも該光輝性インキ層１３の伸展抑制樹脂層１２の側とは反対側の面に凹凸形状１４を有し、該伸展抑制樹脂層１２を形成する樹脂がガラス転移温度８０℃以上の樹脂Ａを含むものである。本発明の水圧転写フィルム製造用転写箔１０は、熱に弱い水溶性フィルムを基材として積層して水圧転写フィルムを得る前の段階で、凹凸形状１４が賦型されているので、凹凸賦型性に劣るという水圧転写フィルムに特有の問題を解消することができる。また、水圧転写フィルムは、水溶性を有する樹脂フィルムを基材として用いることにより、長期保管した場合に空気中の水分を吸収してカーリングやブロッキングを起こしたり、フィルムが伸縮することで意匠性に悪影響を与えるという懸念がある。しかし、本発明の水圧転写フィルム製造用転写箔１０は、水圧転写フィルムの基材として用いる水溶性フィルムと分離した状態で保管し、使用の直前に水圧転写フィルムを容易に作製することができるため、これらの問題を回避することもできる。
[Transfer foil for hydraulic transfer film production]
Hereinafter, the transfer foil for producing a hydraulic transfer film of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a transfer foil for producing a hydraulic transfer film of the present invention.
The
（剥離フィルム）
剥離フィルムは、伸展抑制樹脂層や、必要に応じて好ましく設けられる剥離層と接触した後でも剥離することができるフィルムであればよく、特に制限されるものではないが、非水溶性を有するものや、良好な凹凸形状を形成する観点からは耐熱性の高いものが好ましい。具体的には、ポリエチレンテレフタレートなどのポリエステル樹脂フィルム、あるいはポリエチレンフィルムやポリプロピレンフィルムなどのポリオレフィン樹脂フィルムや延伸ポリオレフィン樹脂フィルムのほか、紙類、又はそれらをシリコーンなどの離型剤でコーティングして、易剥離処理したものなどが好ましく挙げられる。これらのなかでも、ポリエステル樹脂フィルム、延伸ポリオレフィン樹脂フィルムが好ましく、さらにポリエステル樹脂フィルム、とりわけポリエチレンテレフタレート樹脂フィルムが好ましい。
また、伸展抑制樹脂層や剥離層と剥離しやすいものを選定する観点からは、易剥離処理したものを用いることが好ましい。
(Peeling film)
The release film is not particularly limited as long as it is a film that can be peeled off even after coming into contact with the extension suppressing resin layer or a release layer that is preferably provided as necessary. In addition, from the viewpoint of forming a good uneven shape, those having high heat resistance are preferable. Specifically, in addition to a polyester resin film such as polyethylene terephthalate, a polyolefin resin film such as a polyethylene film or a polypropylene film, or a stretched polyolefin resin film, paper, or coating them with a release agent such as silicone, Preferable examples include those subjected to a peeling treatment. Among these, a polyester resin film and a stretched polyolefin resin film are preferable, and a polyester resin film, particularly a polyethylene terephthalate resin film is preferable.
In addition, from the viewpoint of selecting a material that easily peels from the extension suppressing resin layer or the release layer, it is preferable to use a material that has been easily peeled off.
剥離フィルムの厚さは、１０〜１００μｍが好ましい。上記範囲内であると、良好な凹凸形状を設けやすく、また転写箔の生産安定性が高くなる。同様の観点から、剥離フィルムの厚さは、２０〜６０μｍの範囲がより好ましい。 As for the thickness of a peeling film, 10-100 micrometers is preferable. Within the above range, it is easy to provide a good concavo-convex shape, and the production stability of the transfer foil is increased. From the same viewpoint, the thickness of the release film is more preferably in the range of 20 to 60 μm.
（剥離層）
剥離層は、剥離フィルムと伸展抑制樹脂層との間に設けられる層であり、剥離フィルムを剥離しやすくするために好ましく設けられる層である。
剥離層を形成する材料としては、剥離性に優れた樹脂であれば特に制限はなく、例えば、アクリル樹脂、塩酢ビ樹脂（塩化ビニルと酢酸ビニルとの共重合体）、オレフィン樹脂、シリコーン樹脂、フッ素樹脂、ポリビニルピロリドン樹脂、シリコーンあるいはフッ素で変性した各種の樹脂などが好ましく挙げられる。
(Peeling layer)
The release layer is a layer provided between the release film and the stretch-inhibiting resin layer, and is preferably a layer provided in order to facilitate peeling of the release film.
The material for forming the release layer is not particularly limited as long as it is a resin excellent in peelability. For example, an acrylic resin, a vinyl acetate resin (a copolymer of vinyl chloride and vinyl acetate), an olefin resin, a silicone resin. Fluorine resin, polyvinyl pyrrolidone resin, silicone, various resins modified with fluorine, and the like are preferable.
また、これらの樹脂にワックスを配合することもできる。ワックスとしては、転写時に溶融して剥離性を発揮するものであれば特に制限はなく、例えば、マイクロクリスタリンワックス、カルナバワックス、パラフィンワックス、フィッシャートロプシュワックス、各種低分子量ポリエチレン、木ロウ、ミツロウ、鯨ロウ、イボタロウ、羊毛ロウ、セラックワックス、キャンデリラワックス、ペトロラクタム、一部変性ワックス、脂肪酸エステル、脂肪酸アミドなどが好ましく挙げられる。これらのなかでも、比較的融点が高く、かつ溶剤に溶けにくいマイクロクリスタリンワックス及びカルナバワックスなどが好ましい。 Moreover, wax can also be mix | blended with these resin. The wax is not particularly limited as long as it melts at the time of transfer and exhibits releasability. For example, microcrystalline wax, carnauba wax, paraffin wax, Fischer-Tropsch wax, various low molecular weight polyethylene, wood wax, beeswax, whale Preferred examples include wax, ibota wax, wool wax, shellac wax, candelilla wax, petrolactam, partially modified wax, fatty acid ester, and fatty acid amide. Among these, microcrystalline wax and carnauba wax having a relatively high melting point and hardly soluble in a solvent are preferable.
剥離層の厚さは、１〜１０μｍが好ましく、１〜５μｍがより好ましい。剥離層の厚さが上記範囲内であると、良好な剥離性能が得られる。 1-10 micrometers is preferable and, as for the thickness of a peeling layer, 1-5 micrometers is more preferable. When the thickness of the release layer is within the above range, good release performance can be obtained.
（伸展抑制樹脂層）
伸展抑制樹脂層は、剥離フィルムと後述する光輝性インキ層との間に設けられ、伸展抑制樹脂層を形成する樹脂として、ガラス転移温度８０℃以上の樹脂Ａを含むことを要する層である。伸展抑制樹脂層を設けることにより、転写箔の製造時に凹凸形状が良好に賦型しうる賦型性が得られ、また水圧転写時に光輝性インキ層が伸展しすぎるのを抑制し、凹凸形状に対応する凹凸感発現部を形成して凹凸感を保持することで、光輝性と高級感とを備える意匠性（以後、単に意匠性と称する場合がある。）が得られる。なお、凹凸形状に対応する凹凸感発現部については、加飾成形品の製造方法についての説明において詳説する。
(Extension suppressing resin layer)
The extension suppressing resin layer is a layer that is provided between the release film and the glitter ink layer described later, and that requires the resin A having a glass transition temperature of 80 ° C. or higher as the resin that forms the extension suppressing resin layer. By providing a stretch-inhibiting resin layer, it is possible to obtain a moldability that allows the uneven shape to be satisfactorily shaped during the production of the transfer foil. By forming the corresponding uneven feeling expression portion to maintain the uneven feeling, design properties (hereinafter sometimes simply referred to as “design properties”) having glitter and high quality are obtained. In addition, about the uneven | corrugated feeling expression part corresponding to an uneven | corrugated shape, it explains in full detail in description about the manufacturing method of a decorative molded product.
本発明において、伸展抑制樹脂層は、樹脂成形品に転写された後の光輝性インキ層の裏面側に位置する層となり、光輝性インキ層が伸展抑制樹脂層を通して視認されることがない。よって、透明、半透明や不透明、あるいは着色の有無は問わず、所望の意匠に応じて選択することができる。また、伸展抑制樹脂層は単層構成でもよく、二層以上の複層構成であってもよい。 In the present invention, the extension suppressing resin layer is a layer located on the back side of the glitter ink layer after being transferred to the resin molded product, and the glitter ink layer is not visually recognized through the extension suppression resin layer. Therefore, it can be selected according to the desired design regardless of whether it is transparent, translucent, opaque, or colored. In addition, the extension suppressing resin layer may have a single layer structure or a multilayer structure of two or more layers.
伸展抑制樹脂層を形成する樹脂としては、ガラス転移温度８０℃以上の樹脂Ａを含むことを要する。伸展抑制樹脂層を形成する樹脂がガラス転移温度８０℃以上の樹脂Ａを含まないと、優れた賦型性が得られず、優れた意匠性が得られない。ガラス転移温度の上限については特に限定的ではないが、転写加工性（追従性）を良好とする観点から１４５℃以下であることが好ましく、１３０℃以下であることがさらに好ましい。 The resin forming the extension suppressing resin layer needs to contain a resin A having a glass transition temperature of 80 ° C. or higher. If the resin forming the extension suppressing resin layer does not contain the resin A having a glass transition temperature of 80 ° C. or higher, excellent moldability cannot be obtained, and excellent design properties cannot be obtained. The upper limit of the glass transition temperature is not particularly limited, but is preferably 145 ° C. or less, and more preferably 130 ° C. or less from the viewpoint of improving transfer processability (following property).
本発明において、ガラス転移温度は以下のようにして測定したものである。
示差走査熱量計を用いて２００℃まで昇温し、その温度から降温速度１０℃／分で０℃まで冷却した試料を昇温速度１０℃／分で測定した。軟化点より２０℃以上低い温度でピークが観測される場合にはそのピークの温度を、また軟化点より２０℃以上低い温度でピークが観測されずに段差が観測されるときは該段差部分の曲線の最大傾斜を示す接線と該段差の高温側のベースラインの延長線との交点の温度を、ガラス転移温度として読み取った。
In the present invention, the glass transition temperature is measured as follows.
Using a differential scanning calorimeter, the temperature was raised to 200 ° C., and a sample cooled from the temperature to 0 ° C. at a temperature lowering rate of 10 ° C./min was measured at a temperature rising rate of 10 ° C./min. When a peak is observed at a
樹脂Ａとしては、ガラス転移温度８０℃以上であれば特に制限はないが、例えば、アクリル樹脂、アクリルポリオール樹脂、ニトロセルロース樹脂、及び塩化ビニル−酢酸ビニル共重合樹脂などが好ましく挙げられ、なかでもアクリルポリオール樹脂が好ましい。本発明においては、これらの樹脂を単独で又は複数種を組み合わせて用いることができる。
また、樹脂Ａとしては、水圧転写時に光輝性インキ層が過度に伸展することを抑制し、凹凸形状に対応する凹凸感発現部を良好に形成する観点から、非水溶性樹脂を用いることが好ましい。ここで、非水溶性樹脂は、一般に非水溶性を有する樹脂として知られる樹脂を称するものであり、具体的には、樹脂Ａとして好ましく例示したものが挙げられる。
The resin A is not particularly limited as long as it has a glass transition temperature of 80 ° C. or higher. For example, acrylic resins, acrylic polyol resins, nitrocellulose resins, and vinyl chloride-vinyl acetate copolymer resins are preferable. Acrylic polyol resins are preferred. In this invention, these resin can be used individually or in combination of multiple types.
In addition, as the resin A, it is preferable to use a water-insoluble resin from the viewpoint of suppressing the excessive extension of the glitter ink layer at the time of hydraulic transfer and favorably forming the uneven appearance part corresponding to the uneven shape. . Here, the water-insoluble resin refers to a resin generally known as a water-insoluble resin, and specific examples thereof include those preferably exemplified as the resin A.
また、伸展抑制樹脂層を形成する樹脂としては、上記樹脂Ａを含んでいれば、他の樹脂、例えばガラス転移温度８０℃未満の樹脂Ｂを含んでもよい。樹脂Ａと組み合わせて用いる樹脂Ｂとしては、例えばガラス転移温度６０℃以下の樹脂が好ましく、２０℃以下の樹脂がより好ましく、ガラス転移温度１０℃以下の樹脂がさらに好ましい。
このような樹脂Ｂとしては、ポリエチレンやポリプロピレンなどのポリオレフィン樹脂、ウレタン樹脂、アセタール樹脂、アルキッド樹脂が好ましく挙げられ、ウレタン樹脂、アルキッド樹脂が好ましい。ガラス転移温度が低い樹脂Ｂを組み合わせることで、優れた転写加工性（追従性）が得られる。なかでも、樹脂Ａとしてアクリルポリオール樹脂を用いる場合は、ウレタン樹脂と組み合わせることが好ましく、また樹脂Ａとして硝化綿などのニトロセルロース樹脂を用いる場合は、アルキッド樹脂と組み合わせることが好ましい。
Moreover, as resin which forms an extension suppression resin layer, as long as the said resin A is included, you may contain other resin, for example, resin B with a glass transition temperature of less than 80 degreeC. As the resin B used in combination with the resin A, for example, a resin having a glass transition temperature of 60 ° C. or lower is preferable, a resin having a glass transition temperature of 10 ° C. or lower is more preferable, and a resin having a glass transition temperature of 10 ° C. or lower is more preferable.
Preferred examples of the resin B include polyolefin resins such as polyethylene and polypropylene, urethane resins, acetal resins, and alkyd resins, and urethane resins and alkyd resins are preferable. By combining the resin B having a low glass transition temperature, excellent transfer processability (followability) can be obtained. In particular, when an acrylic polyol resin is used as the resin A, it is preferably combined with a urethane resin, and when a nitrocellulose resin such as nitrified cotton is used as the resin A, it is preferably combined with an alkyd resin.
伸展抑制樹脂層を形成する樹脂中の樹脂Ａの含有量は、５０質量％以上であることが好ましく、より好ましくは５０〜９５質量％、さらに好ましくは６０〜９０質量％、特に好ましくは７０〜８５質量％である。樹脂中の樹脂Ａの含有量が上記の範囲内であると、優れた賦型性や意匠性が得られるとともに、優れた転写加工性（追従性）も得られる。 The content of the resin A in the resin forming the extension suppressing resin layer is preferably 50% by mass or more, more preferably 50 to 95% by mass, still more preferably 60 to 90% by mass, and particularly preferably 70 to 90%. It is 85 mass%. When the content of the resin A in the resin is within the above range, excellent moldability and design properties are obtained, and excellent transfer processability (follow-up property) is also obtained.
伸展抑制樹脂層の厚さとしては、０．５〜１０μｍが好ましく、０．５〜５μｍがより好ましく、０．５〜２．５μｍがさらに好ましい。伸展抑制樹脂層の厚さが上記範囲内であれば、優れた賦型性や意匠性が得られるとともに、優れた転写加工性（追従性）も得られる。また、水圧転写時の活性剤の塗布の時間を確保し、より好適に被転写体に転写することができる。 The thickness of the extension suppressing resin layer is preferably 0.5 to 10 μm, more preferably 0.5 to 5 μm, and further preferably 0.5 to 2.5 μm. When the thickness of the extension inhibiting resin layer is within the above range, excellent moldability and design properties can be obtained, and excellent transfer processability (followability) can be obtained. Further, it is possible to secure the time for applying the activator at the time of the hydraulic transfer, and to transfer it to the transfer target more suitably.
（光輝性インキ層）
光輝性インキ層は、光輝性を発現するとともに、少なくとも該光輝性インキ層の伸展抑制樹脂層とは反対側の面に凹凸形状を有することで高級感を発現させる層である。
(Bright ink layer)
The glitter ink layer is a layer that expresses glitter and has a concavo-convex shape on at least the surface of the glitter ink layer opposite to the extension-suppressing resin layer to express a sense of quality.
本発明において、凹凸形状は、少なくとも光輝性インキ層の伸展抑制樹脂層の側とは反対側の面に存在することを要する。本発明の転写箔は、凹凸形状を有し、かつ水圧転写時に該凹凸形状に対応する凹凸感発現部を形成して凹凸感を保持することで、光輝性に加えて高級感を発現しうる。凹凸形状は、図１に示されるように、凹部が光輝性インキ層内に留まるものであってもよいし、伸展抑制樹脂層、さらには剥離フィルムにまで至るものであってもよい。本発明においては、後述する凹凸形状の深さを得て、優れた賦型性や意匠性を得る観点から、凹凸形状は伸展抑制樹脂層及び剥離フィルムまで至るものであることが好ましい。 In the present invention, the concavo-convex shape needs to be present on at least the surface of the glittering ink layer on the side opposite to the extension suppressing resin layer side. The transfer foil of the present invention has a concavo-convex shape and can form a sense of quality in addition to the glitter by forming a concavo-convex sensation expressing part corresponding to the concavo-convex shape during hydraulic transfer. . As shown in FIG. 1, the concave / convex shape may be one in which the concave portion stays in the glittering ink layer, or may extend to the stretch suppressing resin layer and further to the release film. In the present invention, from the viewpoint of obtaining the depth of the concavo-convex shape to be described later and obtaining excellent moldability and designability, it is preferable that the concavo-convex shape extends to the stretch suppressing resin layer and the release film.
凹凸形状の深さとしては、優れた賦型性や意匠性を得る観点から、転写箔の全厚さに対して５〜８０％が好ましく、より好ましくは１０〜７０％であり、さらに好ましくは２０〜６０％である。ここで、本発明において凹凸形状の深さは、凹凸形状の凹部の深さのことである。ここで、凹部の深さは、光輝性インキ層の伸展抑制樹脂層を設ける側とは反対側の面を略直線とみたときの、該直線からの深さの最大値とする。 The depth of the concavo-convex shape is preferably from 5 to 80%, more preferably from 10 to 70%, and still more preferably from the viewpoint of obtaining excellent moldability and design properties, with respect to the total thickness of the transfer foil. 20 to 60%. Here, the depth of the concavo-convex shape in the present invention is the depth of the concavo-convex concave portion. Here, the depth of the concave portion is the maximum value of the depth from the straight line when the surface of the glittering ink layer opposite to the side on which the extension suppressing resin layer is provided is regarded as a substantially straight line.
凹凸形状の周期幅（ピッチ）は、１０〜１００μｍが好ましく、より好ましくは２０〜４０μｍである。凹凸形状の周期幅（ピッチ）が上記範囲内であることにより、優れた賦型性や意匠性が得られる。ここで、本発明において凹凸形状の周期幅（ピッチ）は、隣接する凸部間の離間距離のことである。
また、凹凸形状の幅は、１０〜１００μｍが好ましく、より好ましくは２０〜４０μｍである。凹凸形状の幅が上記範囲内であることにより、優れた賦型性や意匠性が得られる。ここで、本発明において凹凸形状の幅は、凸部自体の幅のことである。
また、凹凸形状は、エンボス加工により好適に設けることができる。
10-100 micrometers is preferable and, as for the periodic width (pitch) of uneven | corrugated shape, More preferably, it is 20-40 micrometers. When the uneven width (pitch) of the irregular shape is within the above range, excellent moldability and design properties can be obtained. Here, in the present invention, the period width (pitch) of the concavo-convex shape is a separation distance between adjacent convex portions.
Moreover, 10-100 micrometers is preferable and, as for the width | variety of an uneven shape, More preferably, it is 20-40 micrometers. When the width of the concavo-convex shape is within the above range, excellent moldability and design properties can be obtained. Here, in this invention, the width | variety of uneven | corrugated shape is the width | variety of convex part itself.
Further, the uneven shape can be suitably provided by embossing.
凹凸形状としては、光輝性意匠表現に応じたものとすればよく、後述する光輝性インキ層の模様との組み合わせに応じて適宜選択すればよく、例えば、万線状溝、木目導管溝、木目年輪模様、砂目模様、石目模様、金属結晶面模様、布目模様、梨地模様、皮絞模様、マット面模様、ヘアライン模様、スピン調模様、文字、記号、幾何学図形などが好ましく挙げられる。 The concavo-convex shape may be according to the glitter design expression, and may be appropriately selected according to the combination with the glitter ink layer pattern to be described later. For example, the line groove, the wood grain conduit groove, the grain Preferable examples include an annual ring pattern, a grain pattern, a stone pattern, a metal crystal surface pattern, a cloth pattern, a satin pattern, a leather pattern, a mat surface pattern, a hairline pattern, a spin tone pattern, characters, symbols, and geometrical figures.
光輝性インキ層は、好ましくはバインダー樹脂と光輝性顔料を含む光輝性インキにより形成される。
バインダー樹脂としては、例えば熱可塑性樹脂が挙げられ、具体例としては、アクリル樹脂、アルキッド樹脂などのポリエステル樹脂、不飽和ポリエステル樹脂、ウレタン樹脂（例えばポリエステルウレタン樹脂）、ポリカーボネート樹脂、塩化ビニル−酢酸ビニル共重合樹脂、ポリビニルブチラールなどのポリビニルアセタール樹脂（ブチラール樹脂）、硝化綿などのニトロセルロース樹脂などが好ましく挙げられ、これらを単独で又は複数種を組み合わせて用いることができる。本発明においては、アルキッド樹脂、硝化綿などのニトロセルロース樹脂が好ましく、これらを混合して用いることがより好ましい。これらのバインダー樹脂を用いると、優れた賦型性が得られる。
The glitter ink layer is preferably formed of glitter ink containing a binder resin and a glitter pigment.
Examples of the binder resin include thermoplastic resins. Specific examples include polyester resins such as acrylic resins and alkyd resins, unsaturated polyester resins, urethane resins (for example, polyester urethane resins), polycarbonate resins, and vinyl chloride-vinyl acetate. Preferable examples include copolymer resins, polyvinyl acetal resins such as polyvinyl butyral (butyral resin), nitrocellulose resins such as nitrified cotton, and the like, and these can be used alone or in combination. In the present invention, nitrocellulose resins such as alkyd resins and nitrified cotton are preferable, and it is more preferable to use a mixture thereof. When these binder resins are used, excellent moldability can be obtained.
光輝性顔料としては、光の干渉によって光輝性を発現しうる顔料であれば特に制限されず、例えば、金属顔料、パール顔料、蓄光性顔料などが好ましく挙げられる。
金属顔料としては、金、銀、白金、パラジウム、ニッケル、銅、アルミニウム、クロム、真鍮、錫などの金属や合金、あるいはこれらの金属酸化物からなるものであり、光輝性が高く、安価である点からアルミニウム、真鍮などの鱗片状箔片からなる金属顔料が好ましい。また、パール顔料としては、酸化チタン又は酸化鉄で被覆された鱗片形状アルミナ顔料、酸化チタン又は酸化鉄で被覆された雲母顔料などが好ましく挙げられる。
The luster pigment is not particularly limited as long as it is a pigment that can exhibit luster by light interference, and preferred examples thereof include metal pigments, pearl pigments, and phosphorescent pigments.
The metal pigment is made of a metal or alloy such as gold, silver, platinum, palladium, nickel, copper, aluminum, chromium, brass, tin, or a metal oxide thereof, and has high glitter and is inexpensive. From the point of view, metal pigments made of scaly foil pieces such as aluminum and brass are preferred. Further, preferred examples of the pearl pigment include a scale-shaped alumina pigment coated with titanium oxide or iron oxide, and a mica pigment coated with titanium oxide or iron oxide.
光輝性顔料の平均粒径は、１〜２０μｍであることが好ましく、３〜１５μｍであることがより好ましい。光輝性顔料の平均粒径が上記範囲内であると、優れた光輝性が得られ、また凹凸形状との組み合わせにより高級感も得られやすい。 The average particle diameter of the glitter pigment is preferably 1 to 20 μm, and more preferably 3 to 15 μm. When the average particle diameter of the glitter pigment is within the above range, excellent glitter can be obtained, and a high-class feeling can be easily obtained by combination with the uneven shape.
また、光輝性インキ層の模様としては、上記の凹凸形状との組み合わせに応じて適宜選択すればよく、木目模様、大理石模様（例えばトラバーチン大理石模様）などの岩石の表面を模した石目模様、布目や布状の模様を模した布地模様、タイル貼模様、煉瓦積模様などがあり、これらを複合した寄木、パッチワークなどの模様などが挙げられる。また、全面に渡って一様に着色したような、いわゆるベタ印刷であってもよい。 Further, the pattern of the glitter ink layer may be appropriately selected according to the combination with the above-described uneven shape, and a grain pattern imitating the surface of a rock such as a wood grain pattern, a marble pattern (for example, a travertine marble pattern), There are fabric patterns imitating fabrics and cloth-like patterns, tiled patterns, brickwork patterns, etc., and patterns such as parquets and patchwork that combine these patterns. In addition, so-called solid printing in which the entire surface is uniformly colored may be used.
光輝性インキ層の厚さとしては、０．５〜５μｍが好ましく、０．５〜３μｍがより好ましく、０．５〜２μｍがさらに好ましい。光輝性インキ層の厚さが上記範囲内であると、優れた賦型性や意匠性が得られるとともに、優れた転写加工性（追従性）も得られる。 The thickness of the glitter ink layer is preferably 0.5 to 5 μm, more preferably 0.5 to 3 μm, and further preferably 0.5 to 2 μm. When the thickness of the glitter ink layer is within the above range, excellent moldability and design properties are obtained, and excellent transfer processability (follow-up property) is also obtained.
（水圧転写フィルム製造用転写箔の製造方法）
本発明の水圧転写フィルム製造用転写箔は、例えば以下のようにして製造することができる。
まず、剥離フィルム上に伸展抑制樹脂層を設ける。伸展抑制樹脂層は、公知の塗布方法又は印刷方法、剥離フィルムとの共押出法、あるいは樹脂フィルムを剥離フィルムにラミネートすることにより剥離フィルムの上に積層される。これらのうち、公知の塗布方法又は印刷方法によることが好ましい。
公知の塗布方法としては、グラビアコート、リバースコートなどが挙げられ、公知の印刷方法としては、グラビア印刷などが挙げられる。
(Method for producing transfer foil for hydraulic transfer film production)
The transfer foil for producing a hydraulic transfer film of the present invention can be produced, for example, as follows.
First, an extension suppressing resin layer is provided on the release film. The extension suppressing resin layer is laminated on the release film by a known coating method or printing method, a co-extrusion method with a release film, or by laminating a resin film on the release film. Among these, it is preferable to use a known coating method or printing method.
Known coating methods include gravure coating and reverse coating, and known printing methods include gravure printing.
また、剥離層を設ける場合は、伸展抑制樹脂層を形成する前に、剥離フィルム上に設ける。剥離層は、上記の伸展抑制樹脂層を形成する方法として挙げた、公知の塗布方法又は印刷方法により形成することが好ましい。 Moreover, when providing a peeling layer, it forms on a peeling film, before forming an extension suppression resin layer. The release layer is preferably formed by a known coating method or printing method mentioned as the method for forming the above-described extension suppressing resin layer.
次に、光輝性インキ層を形成する。光輝性インキ層は、バインダー樹脂と光輝性顔料とを含有する光輝性インキを用い、上記の伸展抑制樹脂層を形成する方法として挙げた、公知の塗布方法又は印刷方法により形成することが好ましい。 Next, a glitter ink layer is formed. The glitter ink layer is preferably formed by a known coating method or printing method mentioned as the method for forming the above-described stretch suppression resin layer using a glitter ink containing a binder resin and a glitter pigment.
次いで、凹凸形状を形成する。凹凸形状の形成は好ましくはエンボス加工により行う。エンボス加工は、通常８０〜１３０℃の温度で、２０〜１００ｔｏｎ／ｍ2、好ましくは２０〜６０ｔｏｎ／ｍ2の圧力を加え、１〜１０分間程度のプレス時間でエンボス加工装置により、あるいはエンボスロールなどによる連続的なエンボス加工により行なわれ、所望する凹凸形状を形成する。
ここで用いられるエンボス版としては、上記の凹凸形状の深さ、周期幅（ピッチ）、及び幅を達成できる寸法を具備するものであれば特に制限はない。通常、エンボス版の凹凸形状の深さは、１０〜８０μｍ程度であり、好ましくは２０〜６０μｍ、より好ましくは３０〜４５μｍである。
Next, an uneven shape is formed. The formation of the concavo-convex shape is preferably performed by embossing. Embossing is usually performed at a temperature of 80 to 130 ° C., applying a pressure of 20 to 100 ton / m 2 , preferably 20 to 60 ton / m 2 , with an embossing device for about 1 to 10 minutes, or an embossing roll Etc. is performed by a continuous embossing process to form a desired uneven shape.
There is no restriction | limiting in particular as an embossing plate used here if the dimension which can achieve the depth of the said uneven | corrugated shape, a period width (pitch), and a width | variety is comprised. Usually, the depth of the uneven shape of the embossed plate is about 10 to 80 μm, preferably 20 to 60 μm, more preferably 30 to 45 μm.
〔水圧転写フィルム〕
本発明の水圧転写フィルムは、水溶性フィルム、光輝性インキ層、及び伸展抑制樹脂層を順に有し、少なくとも該光輝性インキ層の伸展抑制樹脂層の側とは反対側の面に凹凸形状を有し、該伸展抑制樹脂層を形成する樹脂がガラス転移温度８０℃以上の樹脂Ａを含むものである。図２は、本発明の水圧転写フィルムの構成の一例を示す概略断面図である。
図２に示される本発明の水圧転写フィルム２０は、水溶性フィルム２１、光輝性インキ層１３、及び伸展抑制樹脂層１２を順に有し、少なくとも該光輝性インキ層１３の伸展抑制樹脂層１２の側とは反対側の面に凹凸形状１４を有している。また、転写箔が剥離層を有する場合は、剥離層を最表面に有することになる。ここで、伸展抑制樹脂層、光輝性インキ層、及び剥離層の詳細は、上述の水圧転写フィルム製造用転写箔におけるものと同じである。
[Hydraulic transfer film]
The hydraulic transfer film of the present invention has a water-soluble film, a glitter ink layer, and an extension suppressing resin layer in this order, and has an uneven shape on the surface of the glitter ink layer opposite to the extension suppressing resin layer side. And the resin that forms the extension suppressing resin layer contains the resin A having a glass transition temperature of 80 ° C. or higher. FIG. 2 is a schematic cross-sectional view showing an example of the configuration of the hydraulic transfer film of the present invention.
The
（水溶性フィルム）
水溶性フィルムは、本発明の水圧転写フィルムにおいて基材の役割を有し、水圧転写後に加飾成形品を得る際に除去されるものである。水溶性フィルムとしては、水溶性又は水膨潤性を有するものであればよく、従来水圧転写フィルムとして一般に使用されている水溶性フィルムの中から、適宜選択して用いることができる。
水溶性フィルムを構成する樹脂としては、例えばポリビニルアルコール樹脂、デキストリン、ゼラチン、にかわ、カゼイン、セラック、アラビアゴム、澱粉、蛋白質、ポリアクリル酸アミド、ポリアクリル酸ナトリウム、ポリビニルメチルエーテル、メチルビニルエーテルと無水マレイン酸との共重合体、酢酸ビニルとイタコン酸との共重合体、ポリビニルピロリドン、アセチルセルロース、アセチルブチルセルロース、カルボキシメチルセルロース、メチルセルロース、ヒドロキシエチルセルロース、アルギン酸ナトリウムなどの各種水溶性ポリマーが挙げられる。これらの樹脂は、単独で用いられてもよいし、２種以上が混合されて用いられてもよい。なお、水溶性フィルムには、マンナン、キサンタンガム、グアーガムなどのゴム成分が添加されていてもよい。
(Water-soluble film)
The water-soluble film has a role of a substrate in the hydraulic transfer film of the present invention, and is removed when obtaining a decorative molded product after the hydraulic transfer. The water-soluble film is not particularly limited as long as it has water-solubility or water-swelling property, and can be appropriately selected from water-soluble films generally used as a conventional hydraulic transfer film.
Examples of the resin constituting the water-soluble film include polyvinyl alcohol resin, dextrin, gelatin, glue, casein, shellac, gum arabic, starch, protein, polyacrylic amide, sodium polyacrylate, polyvinyl methyl ether, methyl vinyl ether and anhydrous Various water-soluble polymers such as copolymers with maleic acid, copolymers of vinyl acetate and itaconic acid, polyvinylpyrrolidone, acetylcellulose, acetylbutylcellulose, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, sodium alginate and the like can be mentioned. These resins may be used alone or in combination of two or more. In addition, rubber components, such as mannan, xanthan gum, and guar gum, may be added to the water-soluble film.
上記の水溶性フィルムのうち、特に生産安定性と水に対する溶解性及び経済性の点から、ポリビニルアルコール（ＰＶＡ）樹脂フィルムが好ましい。なお、ポリビニルアルコール樹脂フィルムは、ＰＶＡ以外に、澱粉やゴムなどの添加剤を含有していてもよい。
ポリビニルアルコール樹脂フィルムは、ポリビニルアルコールの重合度、ケン化度、及び澱粉やゴムなどの添加剤の配合量などを変えることにより、水溶性フィルムに対して転写用の印刷層を形成する際に必要な機械的強度、取り扱い中の耐湿性、水面に浮かべてからの吸水による柔軟化の速度、水中での延展又は拡散に要する時間、転写工程での変形のし易さなどを適宜調節することができる。
Among the above water-soluble films, a polyvinyl alcohol (PVA) resin film is particularly preferable from the viewpoints of production stability, solubility in water and economy. The polyvinyl alcohol resin film may contain additives such as starch and rubber in addition to PVA.
Polyvinyl alcohol resin film is necessary when forming a printing layer for transfer on a water-soluble film by changing the degree of polymerization of polyvinyl alcohol, the degree of saponification, and the amount of additives such as starch and rubber. The mechanical strength, moisture resistance during handling, speed of softening due to water absorption after floating on the water surface, time required for spreading or diffusion in water, ease of deformation in the transfer process, etc. can be adjusted as appropriate. it can.
ポリビニルアルコール樹脂フィルムからなる水溶性フィルムとして好適なものは、特開昭５４−９２４０６号公報に説明されているようなものであり、例えば、ＰＶＡ樹脂８０質量％、高分子水溶性樹脂１５質量％、澱粉５質量％の混合組成からなり、平衡水分３％程度のものが好適である。
また、ポリビニルアルコール樹脂フィルムは水溶性ではあるが、水に溶解する前段階では水に膨潤して軟化しつつもフィルムとして存続することが好ましい。フィルムとして存続している状態にあるときに水圧転写を行なうことにより、水圧転写時の転写用の印刷層の過度の流動、変形を防止することができるからである。
A suitable water-soluble film comprising a polyvinyl alcohol resin film is as described in JP-A-54-92406, for example, 80% by mass of PVA resin, 15% by mass of polymer water-soluble resin. A composition having a mixed composition of 5% by mass of starch and having an equilibrium water content of about 3% is preferable.
Further, although the polyvinyl alcohol resin film is water-soluble, it is preferable that the film remains as a film while being swollen and softened in water at a stage before being dissolved in water. This is because, by performing the hydraulic transfer while the film is still alive, it is possible to prevent an excessive flow and deformation of the printing layer for transfer during the hydraulic transfer.
水溶性フィルムの厚さとしては、１０〜１００μｍが好ましい。１０μｍ以上であると、フィルムの均一性が良好で、かつ生産安定性が高い。一方、１００μｍ以下であると、水に対する溶解性が適度であり、かつ印刷適性に優れる。以上の観点から、水溶性フィルムの厚さは、２０〜６０μｍの範囲がより好ましい。 As thickness of a water-soluble film, 10-100 micrometers is preferable. When it is 10 μm or more, the uniformity of the film is good and the production stability is high. On the other hand, when it is 100 μm or less, the solubility in water is moderate and the printability is excellent. From the above viewpoint, the thickness of the water-soluble film is more preferably in the range of 20 to 60 μm.
なお、上記の水溶性フィルムは、例えば紙、不織布、布などの水浸透性を有する基材と積層して使用することもできるが、このような水浸透性を有する基材と水溶性又は水膨潤性を有する水溶性フィルムとを積層したときには、水圧転写フィルムを水面に浮かべる前に、水浸透性を有する基材を水溶性又は水膨潤性を有する水溶性フィルムから分離させるか、又は水面に浮かべた後の水の作用によって水溶性又は水膨潤性を有する水溶性フィルムから水浸透性を有する基材が分離するように構成しておくことが好ましい。 The water-soluble film can be used by being laminated with a water-permeable base material such as paper, nonwoven fabric, and cloth, for example. When laminating a water-soluble film having swellability, before the hydraulic transfer film floats on the water surface, the substrate having water permeability is separated from the water-soluble or water-soluble film having water swellability, or on the water surface. It is preferable that the substrate having water permeability is separated from the water-soluble film having water solubility or water swellability by the action of water after floating.
〔水圧転写フィルムの製造方法〕
本発明の水圧転写フィルムの製造方法は、工程（Ａ）剥離フィルム、伸展抑制樹脂層、及び光輝性インキ層を順に有し、少なくとも該光輝性インキ層の伸展抑制樹脂層の側とは反対側の面に凹凸形状を有し、該伸展抑制樹脂層を形成する樹脂がガラス転移温度８０℃以上の樹脂Ａを含む水圧転写フィルム製造用転写箔の光輝性インキ層及び／又は水溶性フィルムに活性剤を塗布する工程、工程（Ｂ）該転写箔の光輝性インキ層側に該水溶性フィルムを積層する工程、及び工程（Ｃ）剥離フィルムを剥離する工程を順に有することを特徴とするものである。
[Method for producing hydraulic transfer film]
The method for producing a hydraulic transfer film of the present invention comprises a step (A) a release film, an extension suppressing resin layer, and a glittering ink layer in this order, and at least the side of the glittering ink layer opposite to the extension suppressing resin layer side. The surface of the film has an uneven shape, and the resin forming the stretch-inhibiting resin layer is active in the glitter ink layer and / or water-soluble film of the transfer foil for producing a hydraulic transfer film containing the resin A having a glass transition temperature of 80 ° C. or higher. It comprises a step of applying an agent, a step (B) a step of laminating the water-soluble film on the glitter ink layer side of the transfer foil, and a step (C) a step of peeling the release film. is there.
工程（Ａ）において用いられる活性剤としては、光輝性インキ層や水溶性フィルムの表面を荒らして密着しやすくしうるものであれば特に制限なく、例えば後述する活性剤組成物を用いることもできるし、水を用いることもできる。活性剤としては、水を用いることが容易であり、好ましい。 The activator used in the step (A) is not particularly limited as long as the surface of the glittering ink layer or the water-soluble film can be roughened and easily adhered, and for example, an activator composition described later can also be used. However, water can also be used. As the activator, it is easy to use water, which is preferable.
工程（Ｂ）は、水圧転写フィルム製造用転写箔の光輝性インキ層側に水溶性フィルムを重ね合わせて加圧することで、積層することができる。より具体的には、水溶性フィルムと転写箔とを重ね合わせた状態で、２つのロール胴間に導入することで連続的に積層することができる。 A process (B) can be laminated | stacked by superposing | stacking and pressing a water-soluble film on the glittering ink layer side of the transfer foil for hydraulic transfer film manufacture. More specifically, in a state where the water-soluble film and the transfer foil are superposed, they can be continuously laminated by introducing them between two roll cylinders.
さらに、工程（Ｃ）において剥離フィルムを剥離することにより、本発明の水圧転写フィルム、すなわち、水溶性フィルム、光輝性インキ層、及び伸展抑制樹脂層を順に有し、少なくとも該光輝性インキ層の伸展抑制樹脂層の側とは反対側の面に凹凸形状を有し、該伸展抑制樹脂層を形成する樹脂がガラス転移温度８０℃以上の樹脂Ａを含む水圧転写フィルムが得られる。 Further, by peeling the release film in the step (C), the hydraulic transfer film of the present invention, that is, the water-soluble film, the glitter ink layer, and the stretch-inhibiting resin layer are sequentially provided, and at least the glitter ink layer A hydraulic transfer film having a concavo-convex shape on the surface opposite to the side of the stretch-inhibiting resin layer and containing the resin A having a glass transition temperature of 80 ° C. or higher is obtained.
［加飾成形品の製造方法］
本発明の加飾成形品の製造方法は、工程（ａ）水溶性フィルム、光輝性インキ層、及び伸展抑制樹脂層を順に有し、少なくとも該光輝性インキ層の伸展抑制樹脂層の側とは反対側の面に凹凸形状を有し、該伸展抑制樹脂層を形成する樹脂がガラス転移温度８０℃以上の樹脂Ａを含む水圧転写フィルムを該水溶性フィルム側が水面側に向くように水面に浮遊させる前又は後に、該伸展抑制樹脂層に活性剤組成物を塗布する活性剤塗布工程、工程（ｂ）該工程（ａ）を経た水圧転写フィルム上に被転写体を押圧し、水圧によって該伸展抑制樹脂層を被転写体の被転写面に密着させる工程、及び工程（ｃ）該被転写体の被転写面に密着した水溶性フィルムを除去する脱膜工程を順に有することを特徴とするものである。
[Method of manufacturing decorative molded product]
The method for producing a decorative molded product of the present invention includes a step (a) a water-soluble film, a glittering ink layer, and an extension suppressing resin layer in this order, and at least the extension inhibiting resin layer side of the glittering ink layer. The opposite surface has a concavo-convex shape, and the resin that forms the stretch-inhibiting resin layer floats on the water surface such that the water-soluble film side faces the water surface side, with the water transfer film containing resin A having a glass transition temperature of 80 ° C. or higher. Before or after the activator, an activator application step of applying an activator composition to the stretch-inhibiting resin layer, step (b) pressing the transferred object onto the hydraulic transfer film that has undergone the step (a), and the extension by water pressure A step of closely attaching the suppression resin layer to the transfer surface of the transferred body, and a step (c) a film removal step of removing the water-soluble film adhered to the transfer surface of the transferred body. It is.
図３は、本発明の加飾成形品の製造方法により得られる加飾成形品の構成の一例を示す概略断面図であり、図２に示される水圧転写フィルムを用いた際の加飾成形品を示すものである。図３に示される、本発明の加飾成形品の製造方法により得られる加飾成形品３０は、被転写体３１、伸展抑制樹脂層１２、及び光輝性インキ層１３を順に有している。そして、光輝性インキ層１３の凹凸形状１４に対応する凹部状の凹凸感発現部３３を有することで、凹凸感が保持されており、これにより加飾成形品３０は光輝性と高級感とを備える意匠性を有するものとなっている。また、加飾成形品３０には、必要に応じてトップコート層３２を設けることもできる。
FIG. 3 is a schematic cross-sectional view showing an example of the configuration of a decorative molded product obtained by the method of manufacturing a decorative molded product of the present invention, and a decorative molded product when using the hydraulic transfer film shown in FIG. Is shown. The decorative molded
凹凸形状に対応する凹凸感発現部は、水圧転写の際に、本発明の水圧転写フィルムが若干伸展することにより、凹凸形状が全体的に緩やかな形状となり形成されるものであり、視覚的に凹凸感を保持するものである。本発明の水圧転写フィルムは、水圧転写の際に適度に伸展し、凹凸感発現部を形成することで、凹凸感を保持することとなり、優れた転写加工性（追従性）とともに、優れた意匠性をも得られる。 The unevenness-expressing portion corresponding to the uneven shape is formed so that the uneven shape becomes a gentle shape as a whole when the hydraulic transfer film of the present invention is slightly stretched during the hydraulic transfer. It retains the feeling of unevenness. The hydraulic transfer film of the present invention is moderately stretched during hydraulic transfer and forms an uneven feeling expression part to maintain the uneven feeling, and has an excellent design with excellent transfer processability (following property). Sex is also obtained.
（活性剤塗布工程（ａ））
活性剤塗布工程（ａ）は、水圧転写フィルムを水面に浮遊させる前又は後に、伸展抑制樹脂層に活性剤組成物を塗布する工程である。この工程で、伸展抑制樹脂層に活性剤を塗布することにより、該伸展抑制樹脂層の表面が荒れ、被転写体と密着しやすくなる。
水圧転写フィルムは、水溶性フィルム側が水面側に向くように水面上に浮遊させる。水圧転写フィルムを水面に浮遊させるには、枚葉の印刷物を１枚ずつ浮遊させてもよく、また水を一方向に流し、その水面上に連続帯状の水圧転写フィルムを、連続的に供給して浮遊させてもよい。
(Activator application process (a))
The activator application step (a) is a step of applying the activator composition to the extension inhibiting resin layer before or after the hydraulic transfer film is floated on the water surface. In this step, by applying the activator to the extension suppressing resin layer, the surface of the extension suppressing resin layer is roughened, and it becomes easy to adhere to the transfer target.
The hydraulic transfer film is floated on the water surface so that the water-soluble film side faces the water surface side. In order to float the hydraulic transfer film on the surface of the water, it is possible to float one sheet of printed matter at a time, or to flow water in one direction and continuously supply a continuous belt-like hydraulic transfer film on the surface of the water. May be suspended.
活性剤組成物は、水圧転写フィルムの伸展抑制樹脂層を荒らすことができ、かつ後述する被転写体の表面を溶解させる機能を有する組成物であれば特に制限はなく、また、被転写体の被転写面に伸展抑制樹脂層、及び光輝性インキ層を転写させるまで蒸発しないような性状を有することが好ましい。このような活性剤組成物としては、例えばエステル類、アセチレングリコール類、エーテル類、及び樹脂を含む組成物が好ましく挙げられる。 The activator composition is not particularly limited as long as it is a composition that can roughen the extension-suppressing resin layer of the hydraulic transfer film and has a function of dissolving the surface of the transfer target described later. It is preferable to have such a property that it does not evaporate until the extension suppressing resin layer and the glitter ink layer are transferred to the transfer surface. As such an activator composition, the composition containing ester, acetylene glycol, ethers, and resin is mentioned preferably, for example.
エステル類としては、酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸イソブチル、酢酸ｓｅｃ−ブチル、酢酸ｔｅｒｔ−ブチル、シュウ酸ジブチル、フタル酸ジブチル、フタル酸ジメチル、フタル酸ジオクチル、フタル酸ジイソオクチルなどが好ましく挙げられる。
アセチレングリコール類としては、メトキシブチルアセテート、エトキシブチルアセテート、エチルカルビトールアセテート、プロピルカルビトールアセテート、ブチルカルビトールアセテートなどが好ましく挙げられる。
エーテル類としては、メチルセロソルブ、ブチルセロソルブ、イソアミルセロソルブなどが好ましく挙げられる。
また、樹脂としては、アクリレート系単量体の単独又は共重合体などの熱可塑性樹脂や、ポリアミド樹脂、ポリエステル樹脂、フェノール樹脂、メラミン樹脂、尿素樹脂、エポキシ樹脂、フタル酸アルキッド樹脂、フタル酸ジアリル樹脂、アルキッド樹脂、ポリウレタン樹脂などの熱硬化性樹脂などが好ましく挙げられ、なかでも熱硬化性樹脂が好ましい。
Preferred examples of esters include ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, dibutyl oxalate, dibutyl phthalate, dimethyl phthalate, dioctyl phthalate, and diisooctyl phthalate. It is done.
Preferred examples of acetylene glycols include methoxybutyl acetate, ethoxybutyl acetate, ethyl carbitol acetate, propyl carbitol acetate, and butyl carbitol acetate.
Preferred examples of ethers include methyl cellosolve, butyl cellosolve, and isoamyl cellosolve.
In addition, as resins, thermoplastic resins such as acrylate monomers alone or copolymers, polyamide resins, polyester resins, phenol resins, melamine resins, urea resins, epoxy resins, alkyd phthalate resins, diallyl phthalates Preferred examples include thermosetting resins such as resins, alkyd resins, and polyurethane resins, and among these, thermosetting resins are preferred.
本発明で用いられる活性剤組成物の好ましい各組成の含有量は、エステル類は５〜４０質量％、アセチレングリコール類は４０〜８０質量％、エーテル類は５〜３０質量％、及び樹脂は１〜２０質量％程度である。 The content of each preferable composition of the activator composition used in the present invention is 5 to 40% by mass for esters, 40 to 80% by mass for acetylene glycols, 5 to 30% by mass for ethers, and 1 for resin. About 20% by mass.
活性剤組成物の塗布は、スプレーコート法などにより行えばよく、その塗布量は通常１〜５０ｇ／ｍ2であり、好ましくは３〜３０ｇ／ｍ2であり、さらに好ましくは１０〜２０ｇ／ｍ2である。 The activator composition may be applied by spray coating or the like, and the application amount is usually 1 to 50 g / m 2 , preferably 3 to 30 g / m 2 , more preferably 10 to 20 g / m 2. 2 .
（工程（ｂ））
工程（ｂ）は、工程（ａ）を経た水圧転写フィルム上に被転写体を押圧し、水圧によって伸展抑制樹脂層を被転写体の被転写面に密着させる工程である。
水圧転写フィルムを浮かべ水圧を印加するための水は、水溶性フィルムの種類などに応じ、適宣水温を調整するのがよく、好ましくは２５〜５０℃程度、より好ましくは２５〜３５℃である。
また、本発明の水圧転写フィルムと被転写体との転写時間は、２０〜１２０秒程度が好ましく、より好ましくは３０〜６０秒程度である。ここで、転写時間とは、本発明の転写フィルムを水に浮遊させてから、被転写体への転写が完了するまでの時間のことである。
(Process (b))
The step (b) is a step of pressing the transferred body onto the hydraulic transfer film that has undergone the step (a), and bringing the extension suppressing resin layer into close contact with the transferred surface of the transferred body by the hydraulic pressure.
The water for applying the floating water pressure to the hydraulic transfer film should be adjusted to an appropriate water temperature according to the type of the water-soluble film, and is preferably about 25 to 50 ° C, more preferably 25 to 35 ° C. .
The transfer time between the hydraulic transfer film of the present invention and the transfer target is preferably about 20 to 120 seconds, more preferably about 30 to 60 seconds. Here, the transfer time is the time from when the transfer film of the present invention is suspended in water until the transfer to the transfer target is completed.
（被転写体）
被転写体としては、例えば、ポリスチレン樹脂、アクリロニトリル−ブタジエン−スチレン共重合樹脂（ＡＢＳ樹脂）、ポリカーボネート樹脂、メラミン樹脂、フェノール樹脂、尿素樹脂、繊維系樹脂、ポリエチレン、ポリプロピレンなどの樹脂、あるいはこれらを混合した樹脂のほか、鉄、アルミニウム、銅などの金属、陶磁器、ガラス、琺瑯などのセラミックス、木材などの材料からなる構造体を使用することができる。
(Transfer material)
Examples of the material to be transferred include polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate resin, melamine resin, phenol resin, urea resin, fiber resin, polyethylene, polypropylene, and the like. In addition to the mixed resin, a structure made of a material such as a metal such as iron, aluminum, or copper, ceramics such as ceramics, glass, or wood, or wood can be used.
被転写面の形状は、平面形状である二次元形状であってもよいし、凹凸形状や曲面形状などの三次元形状であってもよい。これらの中で、通常、樹脂製構造体が多用される。この樹脂製構造体は、成形時において離型剤が付着するとともに、ゴミや脂分なども付着することがあり、水圧転写フィルムの光輝性インキ層を密着性よく転写させるために、予め脱脂液により被転写面を清浄化しておくことが好ましい。 The shape of the transfer surface may be a two-dimensional shape that is a planar shape, or a three-dimensional shape such as an uneven shape or a curved shape. Of these, resin structures are usually used frequently. This resin structure has a release agent attached at the time of molding, and dust and fat may also adhere. In order to transfer the glitter ink layer of the hydraulic transfer film with good adhesion, a degreasing liquid is used in advance. It is preferable to clean the surface to be transferred.
工程（ｂ）において、伸展抑制樹脂層上に塗布した活性剤組成物は被転写体と接し、該被転写体の表面を溶解させることで、本発明の転写フィルムと被転写体との密着性は良好なものとなる。 In the step (b), the activator composition applied on the stretch-inhibiting resin layer is in contact with the member to be transferred, and the surface of the member to be transferred is dissolved, whereby the adhesion between the transfer film of the present invention and the member to be transferred is obtained. Will be good.
（脱膜工程（ｃ））
脱膜工程（ｃ）は、被転写体の被転写面に密着した水溶性フィルムを除去する工程である。
水溶性フィルムの除去は、例えば、水を用いてシャワー洗浄することで行うことができる。この工程（ｃ）により、被転写面に付着している水溶性フィルムは除去される。なお、シャワー洗浄の条件は、水溶性フィルムを形成する材料などにより異なるが、通常は水温１５〜６０℃程度、洗浄時間１０秒〜５分程度が好ましい。そして、工程（ｃ）の後、被転写体を十分乾燥し水分を蒸発させれば、被転写体の被転写面に転写された光輝性インキ層と伸展抑制樹脂層とによって、所望の意匠が付与された樹脂成形品が得られる。
(Film removal step (c))
The film removal step (c) is a step of removing the water-soluble film adhered to the transfer surface of the transfer object.
The water-soluble film can be removed by, for example, shower cleaning using water. By this step (c), the water-soluble film adhering to the transfer surface is removed. The shower cleaning conditions vary depending on the material forming the water-soluble film, but usually a water temperature of about 15 to 60 ° C. and a cleaning time of about 10 seconds to 5 minutes are preferable. And after a process (c), if a to-be-transferred body is fully dried and a water | moisture content is evaporated, a desired design will be carried out by the glittering ink layer and the extension suppression resin layer which were transcribe | transferred to the to-be-transferred surface of the to-be-transferred body. The assigned resin molded product is obtained.
（工程（ｄ））
本発明の加飾成形品の製造方法は、工程（ｃ）の後、さらに所望により、転写された光輝性インキ層上に、トップコート層を形成する工程（ｄ）を有することができる。
工程（ｄ）において、前記工程（ｃ）にて被転写体の被転写面に転写された光輝性インキ層に対し、表面強度向上、表面保護、表面艶調整などのために、必要に応じてトップコート剤を塗布して、トップコート層を形成することができる。トップコート剤としては、例えば熱可塑性樹脂、熱硬化性樹脂、紫外線硬化性樹脂など、具体的にはウレタン樹脂、エポキシ樹脂、アクリル樹脂、フッ素樹脂、ケイ素樹脂などを含む樹脂組成物が好ましく挙げられる。
(Process (d))
The method for producing a decorative molded product of the present invention may further include a step (d) of forming a topcoat layer on the transferred glittering ink layer, if desired, after the step (c).
In the step (d), for the glitter ink layer transferred to the transfer surface of the transfer body in the step (c), for the purpose of improving the surface strength, protecting the surface, adjusting the surface gloss, etc., as necessary A topcoat agent can be applied to form a topcoat layer. As the top coat agent, for example, a thermoplastic resin, a thermosetting resin, an ultraviolet curable resin, and the like, specifically, a resin composition containing a urethane resin, an epoxy resin, an acrylic resin, a fluororesin, a silicon resin, and the like are preferable. .
トップコート層は、これらの樹脂組成物を塗装し、硬化させて形成することができる。塗装方法としては、スプレー塗装、静電塗装、刷毛塗り、浸漬塗装など公知の方法を用いることができる。また、硬化させる方法としては、使用する樹脂組成物により適宜選定すればよく、熱可塑性樹脂を用いる場合は数日間養生すればよく、熱硬化性樹脂を用いる場合は熱処理を行えばよく、紫外線硬化性樹脂を用いる場合は適切な紫外線を照射して行えばよい。 The top coat layer can be formed by coating and curing these resin compositions. As a coating method, known methods such as spray coating, electrostatic coating, brush coating, and dip coating can be used. In addition, the curing method may be appropriately selected depending on the resin composition to be used. If a thermoplastic resin is used, it may be cured for several days. If a thermosetting resin is used, heat treatment may be performed. In the case of using a functional resin, it may be performed by irradiating with an appropriate ultraviolet ray.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
（１）賦型性の評価
各例における水圧転写フィルム製造用転写箔の光輝性インキ層にエンボス加工（エンボス条件：温度１２０℃、圧力４０ｔｏｎ／ｍ2、プレス時間５分）を施して、エンボス版を剥がした後の、該光輝性インキ層の表面の様子を目視により観察し、下記の基準で評価した。
◎：光輝性インキ層が剥がれることなく、凹凸形状が極めて深く、明瞭に賦型されていた。
○：光輝性インキ層が剥がれることなく、凹凸形状が良好に賦型されていた。
△：熱い状態では光輝性インキ層が若干剥がれるものの、室温まで冷やした後にエンボス版を剥がすと、光輝性インキ層は剥がれることなく、凹凸形状が実用にあたり問題が生じない程度に賦型されていた。
×：室温まで冷やした後にエンボス版を剥がしても、光輝性インキ層が剥がれてしまい、凹凸形状を賦型することができなかった。
（２）意匠性の評価
各例により得られた水圧転写フィルムの伸展抑制樹脂層に、下記組成の活性剤組成物を３ｇ／ｍ2塗布し、スムージングロールで該活性剤組成物を均一にし、伸展抑制樹脂層の活性剤塗布工程（ａ）を経た後、水圧転写フィルムに被転写体を押圧し、水圧によって伸展抑制樹脂層を被転写体の被転写面に密着させる工程（ｂ）、及び水洗による脱膜工程（ｃ）を経て、加飾成形品を得た。得られた加飾成形品を目視により観察し、その意匠性について以下の基準で評価した。
（活性剤組成物の組成）
フタル酸系アルキッド樹脂 ６質量部
マイクロシリカ（顔料） ２質量部
フタル酸ジブチル １７質量部
溶剤（ブチルカルビトールアセテート） ６０質量部
溶剤（ブチルセロソルブ） １５質量部
◎：光輝性インキ層の凹凸形状に対応する凹凸感が極めて良好に保持されており、非常に優れた光輝性と高級感が得られた。
○：光輝性インキ層の凹凸形状に対応する凹凸感が良好に保持されており、優れた光輝性と高級感が得られた。
△：光輝性インキ層の凹凸形状に対応する凹凸感がやや低下したものの十分視認でき、実用にあたり問題が生じない程度の光輝性と高級感が得られた。
×：光輝性インキ層の凹凸形状に対応する凹凸感が消失したため、光輝性と高級感とが得られない、または水圧転写フィルムの製造の時点で凹凸形状を賦型できなかった。
（３）転写加工性（追従性）の評価
加飾成形品の製造において、被転写体として、直径３５ｍｍ、長さ２５０ｍｍの円柱形状の樹脂成形体を用い、その側面に水圧転写フィルムを転写させた際の水圧転写フィルムの転写加工性（追従性）について、目視による観察により、以下の基準で評価した。
◎：被転写体に良好に追従し、割れを一切生じることなく加飾成形品が得られた。
○：水圧転写フィルムの伸展性が若干悪く、割れや付き回り性に若干劣るものの、意匠性にほとんど影響を与えることなく転写加工を行うことができた。
△：水圧転写フィルムの伸展性が若干悪く、割れや付き回り性に劣るものの、意匠感への影響は実用にあたり問題が生じない程度のものであった。
×：水圧転写フィルムの伸展性が悪く、割れが著しい加飾成形品となった、あるいは水圧転写時に水圧転写フィルムが割れるなどして被転写体に転写することができなかった。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
(1) Evaluation of formability Embossing (embossing conditions: temperature 120 ° C., pressure 40 ton / m 2 , press time 5 minutes) was performed on the glittering ink layer of the transfer foil for producing a hydraulic transfer film in each example, and embossed. The state of the surface of the glitter ink layer after peeling off the plate was visually observed and evaluated according to the following criteria.
(Double-circle): The uneven | corrugated shape was very deep and it was shape | molded clearly, without the glittering ink layer peeling.
○: The uneven shape was satisfactorily shaped without peeling off the glitter ink layer.
Δ: The glittering ink layer peeled off slightly in the hot state, but when the embossed plate was peeled off after cooling to room temperature, the glittering ink layer was not peeled off, and the uneven shape was shaped to the extent that no problem occurred in practical use .
X: Even if the embossed plate was peeled off after cooling to room temperature, the glittering ink layer was peeled off, and the uneven shape could not be formed.
(2) Evaluation of designability 3 g / m 2 of an activator composition having the following composition was applied to the stretch-suppressing resin layer of the hydraulic transfer film obtained in each example, and the activator composition was made uniform with a smoothing roll. (B) after passing through the activator application step (a) of the stretch-inhibiting resin layer, pressing the transferred body against the hydraulic transfer film, and bringing the stretch-inhibiting resin layer into close contact with the transferred surface of the transferred body by water pressure; A decorative molded product was obtained through a film removal step (c) by washing with water. The obtained decorative molded product was observed visually, and its design property was evaluated according to the following criteria.
(Composition of activator composition)
Phthalic acid-based alkyd resin 6 parts by weight Microsilica (pigment) 2 parts by weight Dibutyl phthalate 17 parts by weight Solvent (butyl carbitol acetate) 60 parts by weight Solvent (butyl cellosolve) 15 parts by weight ◎: Corresponds to the uneven shape of the glitter ink layer The feeling of unevenness is maintained very well, and very excellent glitter and luxury are obtained.
○: The unevenness corresponding to the uneven shape of the glitter ink layer was well maintained, and excellent glitter and luxury were obtained.
(Triangle | delta): Although the uneven | corrugated feeling corresponding to the uneven | corrugated shape of a glittering ink layer was somewhat reduced, it was able to visually recognize enough and the glossiness and high-grade feeling of the grade which does not produce a problem in practical use were obtained.
X: Since the unevenness | corrugation corresponding to the uneven | corrugated shape of a glittering ink layer lose | disappeared, glossiness and a high-class feeling were not obtained, or the uneven | corrugated shape could not be shaped at the time of manufacture of a hydraulic transfer film.
(3) Evaluation of transfer processability (followability) In the production of a decorative molded product, a cylindrical resin molded body having a diameter of 35 mm and a length of 250 mm was used as a transfer target, and a hydraulic transfer film was transferred to the side surface. The transfer processability (followability) of the hydraulic transfer film was evaluated by visual observation based on the following criteria.
(Double-circle): The decorative molded product was obtained, following the transferred material well and without causing any cracks.
○: Although the extensibility of the hydraulic transfer film was slightly poor and cracking and throwing power were slightly inferior, the transfer process could be performed with almost no influence on the design.
Δ: Although the extensibility of the hydraulic transfer film was slightly poor and inferior in cracking and throwing power, the influence on the design feeling was such that no problem occurred in practical use.
X: The hydraulic transfer film had poor extensibility and became a decorative molded product with remarkable cracks, or the hydraulic transfer film was cracked during the hydraulic transfer and could not be transferred to the transfer target.
実施例１
剥離フィルムとして、延伸ポリプロピレンフィルム（厚さ：１８μｍ，耐熱温度：１４０℃）を用い、その片面にアクリル樹脂を塗布量３ｇ／ｍ2でグラビアコートし、厚さ２μｍの剥離層を形成した。次いで、該剥離層上に、第１表に記載の伸展抑制樹脂層を形成する樹脂を塗布量３ｇ／ｍ2でグラビアコートして、厚さ１μｍの伸展抑制樹脂層を設け、光輝性インキ（光輝性顔料：アルミペースト，平均粒径：１０μｍ，バインダー樹脂：硝化綿とアルキッド樹脂とを５０：２０で混合した混合物）を、塗布量２ｇ／ｍ2でグラビアコートして、厚さ１μｍの光輝性インキ層を形成した。さらに、エンボス加工装置を用いて、圧力４０ｔｏｎ／ｍ2、温度１２０℃で光輝性インキ層の表面側からエンボス加工して、深さ２０μｍの凹凸形状を形成して水圧転写フィルム製造用転写箔を得た。得られた転写箔について、上記の（１）賦型性の評価を行い、その評価結果を第１表に示す。
Example 1
A stretched polypropylene film (thickness: 18 μm, heat-resistant temperature: 140 ° C.) was used as the release film, and an acrylic resin was gravure coated on the one side with a coating amount of 3 g / m 2 to form a release layer having a thickness of 2 μm. Next, on the release layer, a resin that forms the stretch-inhibiting resin layer described in Table 1 is gravure coated at a coating amount of 3 g / m 2 to provide a 1-μm-thickness-inhibiting resin layer. Glossy pigment: aluminum paste, average particle size: 10 μm, binder resin: a mixture of nitrified cotton and alkyd resin mixed at 50:20) and gravure coated at a coating amount of 2 g / m 2 , and a thickness of 1 μm An ink layer was formed. Further, using an embossing device, embossing is performed from the surface side of the glittering ink layer at a pressure of 40 ton / m 2 and a temperature of 120 ° C. to form a concavo-convex shape with a depth of 20 μm, thereby producing a transfer foil for producing a hydraulic transfer film Obtained. About the obtained transfer foil, said (1) moldability evaluation is performed and the evaluation result is shown in Table 1.
次に、得られた水圧転写フィルム製造用転写箔を、気温２５℃、相対湿度７０％の環境下で１時間保管した後、表面に水を塗布したポリビニルアルコール樹脂フィルム（厚さ：３０μｍ）を、該転写箔の伸展抑制樹脂層側に重ね合わせて加圧して、剥離フィルムである延伸ポリプロピレンフィルムを剥離して水圧転写フィルムを得た。得られた水圧転写フィルムを用いて、（２）意匠性の評価、及び（３）転写加工性（追従性）の評価を行い、その評価結果を第１表に示す。 Next, the obtained transfer foil for producing a hydraulic transfer film was stored for 1 hour in an environment of an air temperature of 25 ° C. and a relative humidity of 70%, and then a polyvinyl alcohol resin film (thickness: 30 μm) coated with water on the surface was used. Then, the transfer foil was superposed on the extension suppressing resin layer side and pressed, and the stretched polypropylene film as a release film was peeled off to obtain a hydraulic transfer film. Using the obtained hydraulic transfer film, (2) designability evaluation and (3) transfer workability (followability) are evaluated, and the evaluation results are shown in Table 1.
実施例２〜６、ならびに比較例１及び２
実施例１において、伸展抑制樹脂層を形成する樹脂を第１表に示される樹脂とした以外は、実施例１と同様にして水圧転写フィルム製造用転写箔、及び水圧転写フィルムを得た。得られた転写箔について、上記の（１）賦型性の評価を行い、その評価結果を第１表に示す。また、得られた水圧転写フィルムを用いて、（２）意匠性の評価、及び（３）転写加工性（追従性）の評価を行い、その評価結果を第１表に示す。
Examples 2-6 and Comparative Examples 1 and 2
In Example 1, a transfer foil for producing a hydraulic transfer film and a hydraulic transfer film were obtained in the same manner as in Example 1 except that the resin forming the extension suppressing resin layer was changed to the resin shown in Table 1. About the obtained transfer foil, said (1) moldability evaluation is performed and the evaluation result is shown in Table 1. Moreover, (2) evaluation of design property and (3) evaluation of transfer workability (follow-up property) are performed using the obtained hydraulic transfer film, and the evaluation results are shown in Table 1.
比較例３
実施例１において、伸展抑制樹脂層を設けなかったこと以外は、実施例１と同様にして水圧転写フィルム製造用転写箔、及び水圧転写フィルムを得た。得られた転写箔について、上記の（１）賦型性の評価を行い、その評価結果を第１表に示す。また、得られた水圧転写フィルムを用いて、（２）意匠性の評価、及び（３）転写加工性（追従性）の評価を行い、その評価結果を第１表に示す。
Comparative Example 3
In Example 1, a transfer foil for producing a hydraulic transfer film and a hydraulic transfer film were obtained in the same manner as in Example 1 except that the extension suppressing resin layer was not provided. About the obtained transfer foil, said (1) moldability evaluation is performed and the evaluation result is shown in Table 1. Moreover, (2) evaluation of design property and (3) evaluation of transfer workability (follow-up property) are performed using the obtained hydraulic transfer film, and the evaluation results are shown in Table 1.
＊２，アクリルポリオール樹脂とウレタン樹脂との混合比（質量比）は８０：２０である。
＊３，硝化綿とアルキッド樹脂との混合比（質量比）は２０：１０である。
＊４，アクリル樹脂と塩化ビニル−酢酸ビニル共重合樹脂との混合比（質量比）は５０：５０である。
* 2. The mixing ratio (mass ratio) of the acrylic polyol resin and the urethane resin is 80:20.
* 3 The mixing ratio (mass ratio) of nitrified cotton and alkyd resin is 20:10.
* 4 The mixing ratio (mass ratio) of the acrylic resin and the vinyl chloride-vinyl acetate copolymer resin is 50:50.
実施例７〜１２、ならびに比較例４〜６
実施例１〜６、ならびに比較例１〜３において、剥離フィルムを延伸ポリエチレンテレフタレート樹脂フィルム（厚さ：２５μｍ，耐熱温度：２００℃）にかえた以外は実施例１〜６、ならびに比較例１〜３と同様にして、各々実施例７〜１２、ならびに比較例４〜６の水圧転写フィルム製造用転写箔、及び水圧転写フィルムを得た。得られた転写箔について、上記の（１）賦型性の評価を行い、その評価結果を第２表に示す。また、得られた水圧転写フィルムを用いて、（２）意匠性の評価、及び（３）転写加工性（追従性）の評価を行い、その評価結果を第２表に示す。
Examples 7-12 and Comparative Examples 4-6
In Examples 1 to 6 and Comparative Examples 1 to 3, Examples 1 to 6 and Comparative Examples 1 to 1 were used except that the release film was changed to a stretched polyethylene terephthalate resin film (thickness: 25 μm, heat-resistant temperature: 200 ° C.). In the same manner as in Example No. 3, transfer foils for producing hydraulic transfer films and hydraulic transfer films of Examples 7 to 12 and Comparative Examples 4 to 6 were obtained. About the obtained transfer foil, said (1) moldability evaluation is performed and the evaluation result is shown in Table 2. Moreover, using the obtained hydraulic transfer film, (2) designability evaluation and (3) transfer workability (followability) are evaluated, and the evaluation results are shown in Table 2.
本発明の水圧転写フィルム製造用転写箔は、転写箔の製造時に凹凸形状が良好に賦型されており、かつ水圧転写フィルムを使用する前に簡単に水圧転写フィルムを作製することができ、得られた水圧転写フィルムは、良好な凹凸形状を有しており、かつ優れた光輝性と高級感とを備える意匠性を樹脂成形品に付与することができる。また、本発明の製造方法により得られる樹脂成形品は、建材のほか、自動車内装材、建材、家具類、電気製品のハウジングなどとして好適に利用することができる。 The transfer foil for producing a hydraulic transfer film of the present invention has a well-shaped uneven shape at the time of producing the transfer foil, and can easily produce a hydraulic transfer film before using the hydraulic transfer film. The obtained hydraulic transfer film has a good concavo-convex shape, and can impart design properties with excellent glitter and high-class feeling to the resin molded product. Moreover, the resin molded product obtained by the manufacturing method of this invention can be utilized suitably as a vehicle interior material, a building material, furniture, a housing of an electric product etc. besides a building material.
１０ 水圧転写フィルム製造用転写箔
１１ 剥離フィルム
１２ 伸展抑制樹脂層
１３ 光輝性インキ層
１４ 凹凸形状
２０ 水圧転写フィルム
２１ 水溶性フィルム
３０ 加飾成形品
３１ 被転写体
３２ トップコート層
３３ 凹凸感発現部
DESCRIPTION OF
Claims (10)
工程（Ａ）剥離フィルム、伸展抑制樹脂層、及び光輝性インキ層を順に有し、少なくとも該光輝性インキ層の伸展抑制樹脂層の側とは反対側の面に凹凸形状を有し、該伸展抑制樹脂層を形成する樹脂がガラス転移温度８０℃以上の樹脂Ａを含む水圧転写フィルム製造用転写箔の光輝性インキ層及び／又は水溶性フィルムに活性剤を塗布する工程
工程（Ｂ）該転写箔の光輝性インキ層側に該水溶性フィルムを積層する工程
工程（Ｃ）剥離フィルムを剥離する工程 The manufacturing method of the hydraulic transfer film which has the following process (A)-(C) in order, and which has a water-soluble film, a glittering ink layer, and an extension suppression resin layer in order.
Step (A) It has a release film, an extension suppressing resin layer, and a glittering ink layer in this order, and has an uneven shape on at least the surface of the glittering ink layer opposite to the extension suppressing resin layer. Step (B) of applying an activator to the glittering ink layer and / or water-soluble film of the transfer foil for producing a hydraulic transfer film, wherein the resin forming the suppression resin layer contains the resin A having a glass transition temperature of 80 ° C. or higher. Step of laminating the water-soluble film on the glitter ink layer side of the foil (C) Step of peeling the release film
工程（ａ）水溶性フィルム、光輝性インキ層、及び伸展抑制樹脂層を順に有し、少なくとも該光輝性インキ層の伸展抑制樹脂層の側とは反対側の面に凹凸形状を有し、該伸展抑制樹脂層を形成する樹脂がガラス転移温度８０℃以上の樹脂Ａを含む水圧転写フィルムを該水溶性フィルム側が水面側に向くように水面に浮遊させる前又は後に、該伸展抑制樹脂層に活性剤組成物を塗布する活性剤塗布工程
工程（ｂ）該工程（ａ）を経た水圧転写フィルム上に被転写体を押圧し、水圧によって該伸展抑制樹脂層を被転写体の被転写面に密着させる工程
工程（ｃ）該被転写体の被転写面に密着した水溶性フィルムを除去する脱膜工程 The manufacturing method of the decorative molded product which has the following process (a)-(c) in order.
The step (a) has a water-soluble film, a glitter ink layer, and an extension suppressing resin layer in order, and has an uneven shape on at least the surface of the glitter ink layer opposite to the extension suppression resin layer, Before or after the hydraulic transfer film containing the resin A containing the resin A having a glass transition temperature of 80 ° C. or higher is floated on the water surface so that the water-soluble film side faces the water surface, the stretch-inhibiting resin layer is active in the stretch-inhibiting resin layer. Activator application step of applying the agent composition (b) The transferred object is pressed onto the hydraulic transfer film that has undergone the step (a), and the extension suppressing resin layer is brought into close contact with the transferred surface of the transferred object by water pressure. (C) film removal process for removing the water-soluble film adhered to the transfer surface of the transfer object
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